CN102686615B - Process for production of syndiotactic alpha-olefin polymer - Google Patents

Process for production of syndiotactic alpha-olefin polymer Download PDF

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CN102686615B
CN102686615B CN 201080057971 CN201080057971A CN102686615B CN 102686615 B CN102686615 B CN 102686615B CN 201080057971 CN201080057971 CN 201080057971 CN 201080057971 A CN201080057971 A CN 201080057971A CN 102686615 B CN102686615 B CN 102686615B
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carbon atoms
polymerization
olefin
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山本昌由
雪田崇史
山下正洋
兼吉宽矛
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三井化学株式会社
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Abstract

本发明的目的在于开发由能够高温聚合的方法以优异聚合活性制造外消旋二单元组分率高且高分子量的间规立构α-烯烃聚合物的制造方法,间规立构α-烯烃聚合物的制造方法的特征在于,在包含(A)通式[1]所示的过渡金属化合物、和(B)选自(b-1)有机铝氧化合物、(b-2)与过渡金属化合物(A)反应形成离子对的化合物和(b-3)有机铝化合物中的至少1种化合物的烯烃聚合用催化剂的存在下,聚合包含1种以上的碳原子数为3~10的α-烯烃和少量乙烯的单体,在聚合温度25℃以上的条件下,将供给聚合器的乙烯的摩尔数设为PE,将碳原子数为3~10的α-烯烃的摩尔数设为PO时,满足0.001≤PE/PO≤0.030。 Object of the present invention is to develop a method for producing a high-temperature polymerization method can be in the racemic diad is high and that of the production of high molecular weight an excellent polymerization activity of syndiotactic α- olefin polymer, syndiotactic olefin α- a method for producing a polymer wherein the transition metal compound comprising (a) represented by general formula [1], and (B) is selected from (b-1) an organoaluminum oxy-compound, (b-2) with the transition metal olefin in the presence of at least one compound of the compound (a) to form compound (b-3) an organoaluminum compound of the ions in the polymerization catalyst, comprising polymerizing one kind or more carbon atoms of the α- 3 ~ 10 when the number of moles of ethylene olefin and a small amount of ethylene monomer at a polymerization temperature of above 25 ℃, the polymerization reactor is supplied to the PE, the number of moles of carbon atoms α- olefins having 3 to 10 to PO meet 0.001≤PE / PO≤0.030.

Description

间规立构Ct-烯烃聚合物的制造方法技术领域 TECHNICAL FIELD syndiotactic olefin polymer Ct-

[0001] 本发明涉及使用包含具有特定结构的过渡金属化合物的茂金属催化剂的间规立构α -烯烃聚合物的制造方法。 [0001] The present invention relates to syndiotactic α comprising a metallocene transition metal catalyst compound having a specific structure - Method for producing an olefin polymer.

背景技术 Background technique

[0002] 作为聚合碳原子数为3~10的α -烯烃、在工业上制造烯烃聚合物的催化剂,已知有齐格勒-纳塔催化剂,特别是作为用于聚合碳原子数为3的丙烯制造聚丙烯的催化剂在世界范围所使用。 [0002] Examples of the polymerizable carbon atoms, α 3 ~ 10 - the olefin, the catalyst for producing olefin polymers in the industry, are known Ziegler - Natta catalysts, in particular as the number of carbon atoms for the polymerization of 3 propylene production of polypropylene catalysts used worldwide. 该齐格勒-纳塔催化剂因为不仅以高活性生成高分子量的聚丙烯,而且能够高度控制丙烯的排列,所以生成的聚丙烯立构规整性高,因此能够以高结晶性得到高熔点的全同立构聚丙烯。 The Ziegler - Natta catalyst with high activity because not only high molecular weight polypropylene, and propylene can be arranged to control the height, so that the generated high stereoregularity polypropylene, it is possible to obtain highly crystalline high melting point of the whole syndiotactic polypropylene. 另一方面,因为催化剂中包含的活性位点存在多种,所以作为问题点可以列举:与全同立构聚丙烯同时副产出丙烯的排列不规则的无规立构聚丙烯,以及在共聚乙烯与碳原子数为3~10的α -烯烃时,聚合物链中包含的α -烯烃的比例变得不均匀,其结果得到的共聚物的组成分布变宽。 On the other hand, since there are multiple active sites of the catalyst contained, as a problem that it may include: polypropylene with isotactic propylene by-produced simultaneously arranged irregularly atactic polypropylene, and the copolymerization ethylene and carbon atoms in α 3 ~ 10 - olefin, the polymer chain comprises the [alpha] - olefin copolymer ratio becomes uneven, which results in a broadened composition distribution.

[0003] 另外,自1980年由W.Kaminsky等发现茂金属催化剂以来,茂金属催化剂也逐渐作为聚合碳原子数为3~10的α -烯烃、在工业上制造烯烃聚合物的催化剂所使用。 [0003] Further, since 1980 the W.Kaminsky found that a metallocene catalyst, a metallocene polymerization catalyst gradually Examples of carbon atoms of α 3 ~ 10 - olefins, a catalyst for producing an olefin polymer as used in the industry. 茂金属催化剂的情况下,因为大多是单一的金属配位化合物,所以与齐格勒-纳塔催化剂不同,茂金属催化剂活性位点均匀,因此在共聚乙烯与碳原子数为3~10的α -烯烃得到的聚合物中包含的α -烯烃的比例变得均匀,故而有能够得到组成分布窄、高品质的共聚物的优点。 In the case of metallocene catalysts, mostly because of a single metal complex compound, the Ziegler - Natta catalysts having different, homogeneous metallocene catalyst active sites, thus the copolymerization of ethylene with carbon atoms of α 3 ~ 10 - [alpha] -olefin polymer obtained contains - olefin ratio becomes uniform, and therefore there can be obtained a narrow composition distribution, high quality copolymer advantages. 另外,通过变换金属配位化合物的配位基结构,就能够高度控制碳原子数为3~10的α -烯烃的排列,例如,在聚合碳原子数为3的丙烯制造聚丙烯时,就具有如下特征:不仅能够与齐格勒-纳塔催化剂同样得到高度全同立构的聚丙烯,而且不副产无规立构聚丙烯。 Further, by changing the ligand structure of the metal complex compound, it is possible to control the height of the carbon atoms of α 3 ~ 10 - olefin arranged, for example, when the number of carbon atoms, the polymerization of propylene to produce polypropylene 3, it has following characteristics: only capable of Ziegler - Natta catalysts the same highly isotactic polypropylene, but no by-product atactic polypropylene.

[0004] 使用茂金属催化剂聚合丙烯制造全同立构聚丙烯时,已知在反应系统内加氢而调节为所希望的分子量。 [0004] The polymerization of propylene using a metallocene catalyst when producing isotactic polypropylene, isotactic known in the hydrogenation reaction system is adjusted to a desired molecular weight. 报道了通过加氢能够提高催化剂活性,并说明这是因为丙烯以2,1-插入的状态而反应停止的催化剂种由氢被再活化(非专利文献I)。 It reported that the catalyst activity can be improved by hydrogenation, and described because propylene and 2,1-insertion state to stop the reaction catalyst species is reactivated by the hydrogen (Non-Patent Document I). 另一方面,因为随着加氢量增加得到的聚丙烯的分子量下降,所以特别在所希望的分子量高时,加氢的有用性也有限度,其应用范围受到限制。 On the other hand, since the molecular weight of the polypropylene obtained with the increase of amount of hydrogen decreases, it is particularly desired when a high molecular weight, hydrogenated usefulness is also limited, its application range is limited.

[0005] 另外,报道了在使用茂金属催化剂制造在丙烯中共聚有少量乙烯的全同立构聚合物(无规聚丙烯)时,随着增加反应系统内添加的乙烯量,催化剂活性提高(非专利文献2)。 此时,因为在生成的全同立构聚丙烯的分子链中包含乙烯单元而聚丙烯的熔点下降,所以特别在所希望的耐热性高时,有乙烯添加量受到限制而且其他物理性质也变化的问题。 At this time, since the ethylene unit comprising isotactic polypropylene, the molecular chains of the polypropylene produced in the melting point depression, it is particularly desired when high heat resistance, there is limited amount of addition of ethylene and other physical properties are also变化的问题。因此,着眼于由该乙烯添加产生的高活性化,提出了减少乙烯添加量的方案(专利文献I)。 具体而言,在使用非交联型、在配位基中具有至少I种2-芳基茚的茂金属催化剂的丙烯聚合反应系统中,如果添加少量乙烯(优选约2wt%以上)则催化剂活性增加。具体而言,在使用非交联型、在配位基中具有至少I种2-芳基茚的茂金属催化剂的丙烯聚合反应系统中,如果添加少量乙烯(优选约2wt%以上)则催化剂活性increase.在本报告的公开例中,与不添加乙烯时比较,在使用双(2-(3,5-二叔丁基苯基)茚基)二氯化锆制造乙烯含量为1.9摩尔%的无规聚丙烯时,虽然活性和分子量提高,但聚合物的熔点从144°C下降为137°C。另外,得到的无规聚丙烯的拉伸特性显示直到高拉伸均匀地变形、从拉伸的高回复那样的弹性体性质。即,在所希望的耐热性高时,没有消除乙烯添加量受到限制而且其它物理性质也变化的问题。另一方面,在1989年报道了能够制造由齐格勒-纳塔催化剂无法得到的高度间规立构的聚丙烯的茂金属催化剂(非专利文献3)。若使用以铝氧烷将第IV族过渡金属化合物活化的茂金属催化剂聚合丙烯,就可以得到高度间规立构的聚丙烯,该第IV族过渡金属化合物以由碳原子将环戊二烯和芴交联得到的异亚丙基(环戊二烯基)(9-芴基)作为配位基。间规立构结构如下所示,在叔碳上结合的取代基(丙烯时为甲基)相互具有在交替方向的“外消旋”的关系,与以下表示的全同立构结构具有的“内消旋”的关系对照。

[0006] [0006]

Figure CN102686615BD00051

[0007] 全同立构聚丙烯 [0007] isotactic polypropylene

[0008] [0008]

Figure CN102686615BD00052

[0009] 间规立构聚丙烯 [0009] The syndiotactic polypropylene

[0010] 通过相邻连接的外消旋链的关系长时间保持,就成为高度间规立构结构的聚合物,在上述报告中,以表示4个外消旋链连续的部分在全体中占有比例的外消旋五单元组分率的指标来表示其程度。 [0010] The connection relation through the adjacent chain racemic holding time, the polymer becomes isotactic structure a high degree, in the above-mentioned report, to represent four successive portions occupied in the whole chain of racemic the five indicators fraction means the ratio of racemic to represent degree. 在报告例中,最高的外消旋五单元组分率为0.86,若将其换算为单纯的外消旋链(外消旋二单元组分率),则为0.96是非常高的值。 In the report of this embodiment, the highest racemic pentad fraction was 0.86, which is converted to a simple if racemic chain (racemic diad fraction), is 0.96 compared to a very high value. 另外,因为高度间规立构的聚合物为结晶性,外消旋二单元组分率和外消旋五单元组分率与聚合物的熔点(熔化温度)成比例关系,所以一般而言越是高度间规立构的聚合物越显示高熔点。 Further, since a high degree of syndiotactic polymer is crystalline, a melting point of racemic diad fraction and the racemic pentad fraction of the polymer (melt temperature) is proportional, in general it is more is a high degree of syndiotactic polymers the melting point display.

[0011] 有如下报道:由该相邻连接的取代基的立体影响,全同立构聚丙烯时,采取以3分子丙烯旋转I周的螺旋状的2级结构并构成晶体,相对于此,间规立构聚丙烯时,通过取代基在交替的方向的影响或由其热经历和应力经历,可以采取螺旋状结构、平面锯齿形结构等多个能量上稳定的晶体结构,另外,可以在一部分晶体结构之间可逆地相转移(非专利文献4)。 [0011] There are reported as follows: Effect perspective connected by the adjacent substituents, when isotactic polypropylene, to take a helical secondary structure to 3 molecules of propylene and constituting the circumferential rotation I crystals, whereas, when the syndiotactic polypropylene isotactic, by the effect of substituents in alternating directions or stress by heat history and experience, can be taken to stabilize the energy of the plurality of helical structures, zigzag planar structure of the crystal structure, further, may be reversible phase transition between a portion of the crystal structure (Non-Patent Document 4). 报道有这样的晶体结构的不同对聚合物材料特性的不同也有很大影响,间规立构聚丙烯具有与全同立构聚丙烯不同特征的热性质、物理性质、机械性质。 Reported such different properties of the polymer material different crystal structure has a great influence, syndiotactic polypropylene with isotactic different thermal properties wherein the syndiotactic polypropylene, physical properties, and mechanical properties. 另外,该间规立构结构和全同立构结构的不同带来的材料特性的不同,在其它α-烯烃聚合物中也可以看到,因此要求有效地制造间规立构结构的聚合物。 Furthermore, different material properties caused by the difference in the syndiotactic and isotactic structure isotactic structure, may be seen in other α- olefin polymer, thus requiring stereoregular polymer structures efficiently produced inter .

[0012] 现有技术文献 [0012] The prior art documents

[0013] 专利文献 [0013] Patent Document

[0014] 专利文献1:日本特表2002 - 505707号公报 [0014] Patent Document 1: Japanese Unexamined 2002-- Publication No. 505707

[0015] 非专利文献 [0015] Non-Patent Document

[0016]非专利文献 I:Macromol., Chem., Rapid Commun., 1993, 14, 97 [0016] Patent Document I:. Macromol, Chem, Rapid Commun, 1993, 14, 97..

[0017]非专利文献 2 =Polymer, 1989,30,1350 [0017] Non-Patent Document 2 = Polymer, 1989,30,1350

[0018]非专利文献 3 J.Am.Chem.Soc.,1988,110,6255 [0018] Non-Patent Document 3 J.Am.Chem.Soc., 1988,110,6255

[0019]非专利文献 4:MacromoIecules, 1993, 26, 5711发明内容 [0019] Non-Patent Document 4: MacromoIecules, 1993, 26, 5711 Disclosure of the Invention

[0020] 发明所要解决的课题 [0020] Problem to be solved by the invention

[0021] 本发明的发明人进行深入研讨的结果,发现了通过使用包含具有特定结构的交联茂金属化合物的烯烃聚合用催化剂,使I种以上的碳原子数为3~10的α -烯烃和少量乙烯以特定的比例在聚合反应气氛下存在,从而聚合活性提高,且生成的间规立构α-烯烃聚合物的分子量也提高,得到高熔点的聚合物的制造方法,从而完成了本发明。 Results [0021] The present inventors conducted thorough research and found that by using an olefin polymerization catalyst comprising a bridged metallocene compound having a specific structure, so that more kinds of I carbon atoms in α 3 ~ 10 - olefins and a small amount of ethylene at a specific ratio in the presence of a polymerization reaction atmosphere, thereby improving the polymerization activity, molecular weight of the syndiotactic α- olefin polymer produced and also to improve, to give a high melting point polymer production process, thereby completing the present invention.

[0022] 用于解决课题的方法 [0022] Methods for Solving the Problem

[0023] 即,本发明为间规立构α -烯烃聚合物的制造方法,其中,在包含(A)下述通式[I ]所示的过渡金属化合物和(B)选自(b-Ι)有机铝氧化合物、(b-2)与过渡金属化合物(A)反应形成离子对的化合物和(b-3)有机铝化合物中的至少I种化合物的烯烃聚合用催化剂的存在下,在聚合温度25°C以上的条件下聚合包含I种以上的碳原子数为3~10的α -烯烃和少量乙烯的单体时,将供给聚合器的乙烯摩尔数设为Pe,将碳原子数为3~10的α -烯烃摩尔数设为P。 [0023] That is, the present invention is a syndiotactic α - method for producing an olefin polymer, wherein the transition metal compound (A) by the following formula [I] and shown in (B) is selected from (B- under iota) an organoaluminum oxy-compound, (b-2) formed in the presence of an olefin polymerization catalyst compound and (b-3) an organoaluminum compound ions of at least I compounds of the transition metal compound (a) is reacted with, in under the polymerization conditions of 25 ° C above the temperature of the polymerization comprising I or more carbon atoms thereof is α 3 ~ 10 - a small amount of ethylene and ethylene-olefin monomers, the polymerization reactor is supplied to the mole number Pe, the number of carbon atoms the number of moles of olefin to P. - of the α 3 ~ 10 时,满足0.001 < ΡΕ/Ρ0 ( 0030。 When satisfied 0.001 <ΡΕ / Ρ0 (0030.

[0024] [0024]

Figure CN102686615BD00061

[0025][通式[I]中,R1H和R4的4个基团选自氢原子、烃基和含硅基,分别相同或不同,R1和R2不相互结合形成环,R3和R4不相互结合形成环。 [0025] [Formula [I],, R1H and R4 four groups selected from a hydrogen atom, a hydrocarbon group and a silicon-containing, the same or different, R1, and R2 are not bonded to each other to form a ring, R3 and R4 are not bonded to each other to form a ring. R5和R6为选自氢原子、碳原子数为2~20的烃基和含硅基中的原子或取代基,相互相同或不同。 R5 and R6 are selected from a hydrogen atom, a hydrocarbon group having a carbon number of 2 to 20 and containing a silicon atom or a substituent group of, the same or different. M选自钛原子、锆原子和铪原子,Q表示卤原子、烃基、碳原子数为10以下的中性的共轭二烯或非共轭二烯、阴离子配位基或能够以孤对电子配位的中性配位基。 M is selected from a titanium atom, a zirconium atom and a hafnium atom, Q represents a halogen atom, a hydrocarbon group, the number of carbon atoms of the conjugated diene neutral conjugated diene of 10 or less, an anionic ligand or a lone pair electron neutral ligand coordinated. j表示I~4的整数,j为2以上时,多个存在的Q相互相同或不同。 When j represents an integer of I to 4, j is 2 or more, plural Q the same or different. ] ]

[0026] 发明的效果 [0026] Effect of the Invention

[0027] 相比于不包含少量乙烯的制造方法,本发明的烯烃聚合物的制造方法,聚合活性和α-烯烃聚合物的分子量提高,且生成的间规立构α-烯烃聚合物维持着高熔点。 [0027] does not include a small amount compared to the method of the production of ethylene, a method for producing an olefin polymer according to the present invention, the polymerization activity and increase in molecular weight α- olefin polymer, and the resulting syndiotactic olefin polymers maintain α- high melting point.

[0028] 另外,如果使用包含本发明的过渡金属化合物的烯烃聚合催化剂,则在工业上可能的温度下的聚合中也能够制造高分子量的间规立构α-烯烃聚合物。 [0028] Further, if the transition metal compound of the present invention comprises an olefin polymerization catalyst, polymerization is industrially possible temperature can also be produced in a high molecular weight syndiotactic α- olefin polymer.

具体实施方式 detailed description

[0029] 以下,在本发明中,关于过渡金属化合物(Α)、有机金属化合物(B)、包含这两种成分的烯烃聚合用催化剂、在该烯烃聚合用催化剂存在下聚合烯烃类的方法,顺次说明用于实施发明的最优方式。 [0029] Here, in the present invention, regarding the transition metal compound ([alpha]), the organometallic compound (B), an olefin polymerization catalyst comprising two components, a method of polymerizing olefins in the presence of the olefin polymerization catalyst, sequentially described best mode embodiment of the invention.

[0030] <过渡金属化合物成分(A) > [0030] <transition metal compound component (A)>

[0031] 过渡金属化合物成分(A)由下述通式[I]所示的过渡金属化合物构成。 [0031] The transition metal compound component (A) [I] composed of the transition metal compounds represented by the following formula. 过渡金属化合物(A)为交联茂金属化合物。 The transition metal compound (A) is a crosslinked metallocene compound. 在将供给聚合器的乙烯的摩尔数设为Pe,将碳原子数为3~10的α -烯烃的摩尔数设为P。 The number of moles of ethylene fed to the polymerization reactor Pe, the number of carbon atoms of α 3 ~ 10 - the number of moles of olefin to P. 时,满足0.001≤ΡΕ/Ρ0 ≤0.030的情况下,过渡金属化合物成分(A)能够以高聚合活性聚合碳原子数为3~10的α-烯烃。 Is satisfied in the case 0.001≤ΡΕ / Ρ0 ≤0.030, the transition metal compound component (A) can be polymerized with high polymerization activities carbon atoms, α- olefins having 3 to 10. 另外,得到的α-烯烃聚合物的α -烯烃链为高度间规立构,均衡地满足高分子量且高熔点。 Further, the resulting α α- olefin polymers - alkylene chain is a high degree of syndiotactic, balanced to meet the high molecular weight, high melting point.

[0032] [0032]

Figure CN102686615BD00071

[0033] 上述式[I]中,R\R2,R3和R4的4个基团选自氢原子、烃基和含硅基,分别相同或不同,R1和R2不相互结合形成环,R3和R4不相互结合形成环。 [0033] The formula [I],, R & lt \ R2, R3 and R4 four groups selected from a hydrogen atom, a hydrocarbon group and a silicon-containing, the same or different, R1, and R2 are not bonded to each other to form a ring, R3 and R4 not bonded to each other to form a ring. 更优选R1和R4为相同原子或相同基团,R2和R3为相同原子或相同基团,特别优选R2和R3为叔丁基。 More preferably R1 and R4 are the same atoms or the same groups, R2 and R3 are the same atoms or the same groups, R2 and R3 are particularly preferably t-butyl.

[0034] 另外,上述式[I]中,R5和R6为选自氢原子、碳原子数为2~20的烃基和含硅基中的原子或取代基,相互相同或不同。 [0034] Further, the above-mentioned formula [I],, R5 and R6 is a hydrogen atom, selected from carbon atoms having 2 to 20 hydrocarbon group and a silicon atom-containing substituent or group, the same or different. 更优选R5和R6为碳原子数为6~20的烃基。 More preferably R5 and R6 is a hydrocarbon group having a carbon number of 6 to 20.

[0035] 作为碳原子数为6~20的烃基,可以列举苯基、萘基等的芳基;邻甲苯基、间甲苯基、对甲苯基、乙基苯基、正丙基苯基、异丙基苯基、正丁基苯基、仲丁基苯基、叔丁基苯基、二甲苯基等的烷基芳基;邻氯苯基、间氯苯基、对氯苯基、氯萘基等的氯芳基;邻溴苯基、间溴苯基、对溴苯基、溴萘基等的溴芳基;溴甲基苯基、二溴甲基苯基等的溴烷基芳基;邻碘苯基、间碘苯基、对碘苯基、碘萘基等的碘芳基;碘甲基苯基、二碘甲基苯基等的碘烷基芳基;苄基、α -苯乙基、β -苯乙基、二苯基甲基、萘基甲基、新苯基等的芳烷基;间氯苄基、对氯苄基、间溴苄基、对溴苄基、间碘苄基、对碘苄基等的卤化苄基等。 [0035] The hydrocarbon group having carbon atoms of 6 to 20 include a phenyl group, a naphthyl group and the like aryl groups; o-tolyl, m-tolyl, p-tolyl, ethylphenyl, n-propylphenyl, i- propylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, xylyl, etc. alkylaryl; o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, chloronaphthalene基等的氯芳基;邻溴苯基、间溴苯基、对溴苯基、溴萘基等的溴芳基;溴甲基苯基、二溴甲基苯基等的溴烷基芳基;邻碘苯基、间碘苯基、对碘苯基、碘萘基等的碘芳基;碘甲基苯基、二碘甲基苯基等的碘烷基芳基;苄基、α -苯乙基、β -苯乙基、二苯基甲基、萘基甲基、新苯基等的芳烷基;间氯苄基、对氯苄基、间溴苄基、对溴苄基、间碘苄基、对碘苄基等的卤化苄基等。

[0036] R1和R4优选为氢原子或碳原子数为6~20的烃基,更优选为氢原子或碳原子数为6~10的芳基,特别优选为氢原子、苯基、邻甲苯基、间甲苯基、对甲苯基、邻氯苯基、间氯 [0036] R1 and R4 are preferably a hydrogen atom or a hydrocarbon group having carbon atoms 6 to 20, more preferably a hydrogen atom or a carbon atoms, an aryl group having 6 to 10, particularly preferably a hydrogen atom, a phenyl group, o-tolyl , m-tolyl, p-tolyl, o-chlorophenyl, m-chloroperbenzoic

苯基、对氯苯基。 Phenyl, p-chlorophenyl group.

[0037] R5和R6分别相同或不同,优选为碳原子数为6~10的芳基或碳原子数为6~10的芳烷基,特别优选为苯基、苄基、间氯苯基、对氯苯基、间氯苄基、对氯苄基。 [0037] R5 and R6 are each the same or different, preferably carbon atoms, an aryl group having 6 to 10 carbon atoms or aralkyl group having 6 to 10, particularly preferably a phenyl group, a benzyl group, a m-chlorophenyl group, p-chlorophenyl, m-chlorobenzyl, p-chlorobenzyl.

[0038] M为钛、错或铪,优选为错或铪,特别优选为错。 [0038] M is titanium, wrong or hafnium, preferably hafnium or wrong, and particularly preferably wrong.

[0039] Q为以相同或不同组合选自卤原子、烃基、阴离子配位基或能够以孤对电子配位的中性配位基中的原子或基团。 [0039] Q is the same or different combinations of atoms selected from halogen, a hydrocarbon group, an anionic ligand or a lone pair of electrons capable of coordinating atoms or groups in a neutral ligand. [0040] 作为卤原子的具体例子,为氟、氯、溴、碘,作为烃基的具体例子,可以列举甲基、乙基、正丙基、异丙基、2-甲基丙基、1,1-二甲基丙基、2,2-二甲基丙基、1,1-二乙基丙基、1_乙基_1_甲基丙基、I,I, 2, 2-四甲基丙基、仲丁基、叔丁基、1,1- 二甲基丁基、 [0040] Specific examples of the halogen atom include fluorine, chlorine, bromine, iodine, and specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1, 1-methylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1_ ethyl _1_ methylpropyl, I, I, 2, 2- tetramethylbutyl propyl, butyl, t-butyl, 1,1-dimethylbutyl,

I, 1,3_三甲基丁基、新戊基、环己基甲基、环己基、1-甲基-1-环己基、S-顺式-或S-反式_ Π 4_1,3- 丁二烯、S-顺式_或S-反式-η 4_1,4- 二苯基-1,3_ 丁二烯、s_顺式-或s-反式-η 4-3-甲基-1,3-戊二烯、S-顺式-或S-反式-η4-1,4_ 二苄基_1,3_ 丁二烯、S-顺式-或S-反式-η 4-2,4-己二烯、S-顺式-或S-反式-η 4-1,3-戊二烯、s_顺式-或 I, 1,3_-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl, S- cis - or trans S- _ Π 4_1,3- butadiene, S- cis-trans or S- _ -η 4_1,4- -1,3_ diphenyl butadiene, s_ cis - or trans -η 4-3- methyl s- - 1,3-pentadiene, S- cis - or trans -η4-1,4_ S- dibenzyl _1,3_ butadiene, S- cis - or trans -η 4-2 S- , 4-hexadiene, S- cis - or trans -η 4-1,3- S- pentadiene, S_ cis - or

S-反式-η4-ι, 4- 二甲苯基-1,3- 丁二烯、S-顺式-或S-反式-η4-ι, 4-双(三甲基甲娃烷基)_1, 3- 丁二烯等。 S- trans -η4-ι, 4- ditolyl-1,3-butadiene, S- cis - or trans S- -η4-ι, 4- bis (trimethylsilyl baby alkyl) _1, 1,3-butadiene and the like.

[0041] 作为阴离子配位基的具体例子,可以列举甲氧基、叔丁氧基、苯氧基等的烷氧基,乙酸酯、苯甲酸酯等的羧酸酯基,甲磺酸酯、甲苯磺酸酯等的磺酸酯基等。 [0041] As specific examples of the anionic ligand group include methoxy, tert-butoxy, phenoxy and the like alkoxy, acetate, benzoate and the like carboxylic acid ester group, methanesulfonic acid esters, such as tosylate sulfonate group and the like. 作为能够以孤对电子配位的中性配位基的具体例子,可以列举三甲基膦、三乙基膦、三苯基膦、二苯基甲基膦等的有机磷化合物,或四氢呋喃、二乙醚、二噁烷、I,2- 二甲氧基乙烷等的醚类。 As specific examples can be a neutral ligand group coordinated to a lone pair of electrons include trimethyl phosphine, triethyl phosphine, triphenyl phosphine, diphenylmethyl phosphine organophosphorus compounds, or tetrahydrofuran, ethers such as diethyl ether, dioxane, I, 2- dimethoxyethane or the like.

[0042] Q的优选形态为卤原子或碳原子数为I~5的烷基。 [0042] Q is preferably a halogen atom to form carbon atoms or an alkyl group of I ~ 5.

[0043] j为I~4的整数,优选为2。 [0043] j is an integer of 1-4 I, preferably is 2.

[0044] 过渡金属化合物(A)及其例示 [0044] The transition metal compound (A) and illustrates

[0045] 以下,例示在本发明中上述通式[I]所示的过渡金属化合物(A)的具体例子,但不特别由此限定本发明的范围。 Specific examples of the transition metal compound (A), [0045] Hereinafter, the present invention is illustrated in the above-mentioned formula [I] illustrated, but not particularly limit the scope of the present invention thereby.

[0046] 作为在本发明中上述通式[I ]所示的过渡金属化合物(A)的具体例子,可以列举二苄基亚甲基(环戊二烯基)(2,7-二甲基-3,6-二叔丁基芴基)二氯化锆[另外也称为1,3-二苯基异亚丙基(环戊二烯基)(2,7-二甲基-3,6-二叔丁基芴基)二氯化锆。 [0046] Specific examples of the transition metal compound (A) [I] of the present invention shown in the above general formula include dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl 3,6-di-tert-fluorenyl) zirconium dichloride [otherwise known as 1,3-diphenyl isopropylidene (cyclopentadienyl) (2,7-dimethyl-3, di-t-butyl-fluorenyl) zirconium dichloride. 在以下省略别名]、二苄基亚甲基(环戊二烯基)(2,7-二(2,4,6-三甲基苯基)-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二(3,5-二甲基苯基)-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7- 二(4-甲基苯基)-3,6- 二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二萘基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二(4-叔丁基苯基)-3,6-二叔丁基芴基)二氯化锆、二苯乙基亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、二(二苯甲基)亚甲基(环戊二烯基)(2,7- 二苯基-3,6- 二叔丁基芴基)二氯化锆、二(枯基)亚甲基(环戊二烯基)(2,7- 二苯基-3,6- 二叔丁基芴基)二氯化锆、二苯基亚甲基(环戊二烯基)(3,6- 二叔丁基芴基)二 Is omitted in the following alias], dibenzylmethylene (cyclopentadienyl) (2,7-bis (2,4,6-trimethylphenyl) -3,6-di-tert-butyl-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride, dibenzylmethylene ( cyclopentadienyl) (2,7-bis (3,5-dimethylphenyl) -3,6-di-tert-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl enyl) (2,7-bis (4-methylphenyl) -3,6-di-tert-butyl-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2, 7-naphthyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-bis (4-t-butylphenyl) 3,6-di-tert-fluorenyl) zirconium dichloride, methylene-diphenyl (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl ) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride, bis ( cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl ) (3,6-di-tert-butylfluorenyl) 化锆、二邻甲苯基亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二间甲苯基亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二对甲苯基亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻氯苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间氯苯基)亚甲基(环戊二烯基)(3,6- 二叔丁基芴基)二氯化锆、二(对氯苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻溴苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间溴苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对溴苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻碘苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间碘苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对碘苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基) Zirconium, di-o-tolyl methylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride, toluene two methylene (cyclopentadienyl) (3 , di-t-butyl-fluorenyl) zirconium dichloride, di-p methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, bis (o-chloroaniline phenyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, bis (m-chlorophenyl) methylene (cyclopentadienyl) (3, di-t-butyl-fluorenyl) zirconium dichloride, bis (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, bis ( o-bromophenyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, bis (m-bromophenyl) methylene (cyclopentadienyl) ( 3,6-di-tert-fluorenyl) zirconium dichloride, bis (p-bromophenyl) methylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride, bis (o-iodophenyl) methylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride, bis (m-iodophenyl) methylene (cyclopentadienyl ) (3,6-di-tert-fluorenyl) zirconium dichloride, bis (p-iodophenyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) 氯化锆、二(邻三氟甲基苯基)亚甲基(环戊二烯基)(3,6- 二叔丁基芴基)二氯化锆、二(间三氟甲基苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对三氟甲基苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(2-萘基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻氯苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间氯苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对氯苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻溴苄基)亚甲基(环戊二烯基)(3,6_ 二叔丁基芴基)二氯化锆、二(间溴苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对溴苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(邻碘苄基)亚甲基(环戊二烯基)(3 Zirconium dichloride, bis (o-trifluoromethylphenyl) methylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride, bis (m-trifluoromethylphenyl ) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, bis (trifluoromethyl) methylene (cyclopentadienyl pair) (3 , di-t-butyl-fluorenyl) zirconium dichloride, bis (2-naphthyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, bis dibenzylmethylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride, bis (o-chlorobenzyl) methylene (cyclopentadienyl) (3,6 - di-tert-fluorenyl) zirconium dichloride, bis (m-chlorobenzyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, bis (p chlorobenzyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, bis (o-bromobenzyl) methylene (cyclopentadienyl) (3 , 6_ di-tert-fluorenyl) zirconium dichloride, bis (m-bromobenzyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, bis ( p-bromobenzyl) methylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride, bis (o-iodobenzyl) methylene (cyclopentadienyl) ( 3 6-二叔丁基芴基)二氯化锆、二(间碘苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对碘苄基)亚甲基(环戊二烯基)(3,6- 二叔丁基芴基)二氯化锆、二(邻甲基苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(间甲基苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、二(对甲基苄基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、(苄基)(苯基)亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆、(苄基)(苯基)亚甲基(环戊二烯基)(2,7- 二苯基-3,6- 二叔丁基芴基)二氯化锆、(苄基)(苯基)亚甲基(环戊二烯基)(2,7-二邻甲苯基-3,6-二叔丁基芴基)二氯化锆、(苄基)(苯基)亚甲基(环戊二烯基)(2,7-二对氯苯基-3,6-二叔丁基芴基)二氯化锆、(对氯苄基)(苯基)亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、(对氯苄基)(苯基)亚甲基( Di-t-butyl-fluorenyl) zirconium dichloride, bis (m-iodobenzyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, bis ( for iodobenzyl) methylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride, bis (o-methylbenzyl) methylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride, di (m-methylbenzyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) dichloride zirconium, bis (p-methylbenzyl) methylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclo pentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3 , di-t-butyl-fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclopentadienyl) (2,7-di-o-tolyl-3,6-di-t-butyl yl fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclopentadienyl) (2,7-p-chlorophenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, (p-chlorobenzyl) (phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride, ( p-chlorobenzyl) (phenyl) methylene ( 戊二烯基)(2,7- 二邻甲苯基-3,6- 二叔丁基芴基)二氯化锆、(对氯苄基)(苯基)亚甲基(环戊二烯基)(2,7- 二对氯苯基-3,6- 二叔丁基芴基)二氯化锆、(苄基)(对氯苯基)亚甲基(环戊二烯基)(2,7- 二苯基-3,6- 二叔丁基芴基)二氯化锆、(苄基)(对氯苯基)亚甲基(环戊二烯基)(2,7-二邻甲苯基-3,6-二叔丁基芴基)二氯化锆、(苄基)(对氯苯基)亚甲基(环戊二烯基)(2,7- 二对氯苯基-3,6- 二叔丁基芴基)二氯化锆、二苯基亚甲基(环戊二烯基)(2,7-二邻甲苯基-3,6-二叔丁基芴基)二氯化锆、二对甲苯基亚甲基(环戊二烯基)(2,7-二邻甲苯基-3,6-二叔丁基芴基)二氯化锆、二(对氯苯基)亚甲基(环戊二烯基)(2,7-二邻甲苯基-3,6-二叔丁基芴基)二氯化锆、二(对三氟甲基苯基)亚甲基(环戊二烯基)(2,7-二邻甲苯基-3,6-二叔丁基芴基)二氯化锆、二(2-萘基)亚甲基(环戊二烯基)(2,7-二邻 Pentadienyl) (2,7-di-o-tolyl-3,6-di-tert-fluorenyl) zirconium dichloride, (p-chlorobenzyl) (phenyl) methylene (cyclopentadienyl ) (2,7-di-t-butyl-p-chlorophenyl-3,6-fluorenyl) zirconium dichloride, (benzyl) (p-chlorophenyl) methylene (cyclopentadienyl) (2 , 7-diphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride, (benzyl) (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-o toluene-3,6-di-tert-fluorenyl) zirconium dichloride, (benzyl) (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-p-chlorophenyl - 3,6-di-tert-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-o-tolyl-3,6-di-tert-fluorenyl) zirconium dichloride, di-p methylene (cyclopentadienyl) (2,7-di-o-tolyl-3,6-di-tert-fluorenyl) zirconium dichloride, bis (p-chlorophenyl yl) methylene (cyclopentadienyl) (2,7-di-o-tolyl-3,6-di-tert-fluorenyl) zirconium dichloride, bis (p-trifluoromethylphenyl) methylene yl (cyclopentadienyl) (2,7-di-o-tolyl-3,6-di-tert-fluorenyl) zirconium dichloride, bis (2-naphthyl) methylene (cyclopentadienyl ) (2,7-di-o 苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二邻甲苯基-3,6-二叔丁基芴基)二氯化锆、二(对氯苄基)亚甲基(环戊二烯基)(2,7-二邻甲苯基-3,6-二叔丁基芴基)二氯化锆、二(对甲基苄基)亚甲基(环戊二烯基)(2,7-二邻甲苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二邻甲苯基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二(邻乙基苯基)_3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻(正丙基)苯基]_3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻(异丙基)苯基]_3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻(正丁基)苯基]_3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7- 二[邻(异丁基)苯基]-3,6- 二叔丁基芴基]二氯化锆、二苄基亚甲基(环 Phenyl 3,6-di-tert-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di-o-tolyl-3,6-di-tert-butyl fluorenyl) zirconium dichloride, di (p-chlorobenzyl) methylene (cyclopentadienyl) (2,7-di-o-tolyl-3,6-di-tert-fluorenyl) zirconium dichloride , bis (p-methylbenzyl) methylene (cyclopentadienyl) (2,7-di-o-tolyl-3,6-di-tert-fluorenyl) zirconium dichloride, dibenzylmethylene A yl (cyclopentadienyl) (2,7-di-o-tolyl-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7-bis (o-ethylphenyl ) _3,6- di-tert-fluorenyl] zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7-bis [o- (n-propyl) phenyl] _3,6- di-tert-fluorenyl] zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7-bis [o- (isopropyl) phenyl] fluorene di-tert-_3,6- yl] zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7-bis [o- (n-butyl) phenyl] _3,6- di-tert-fluorenyl] dichloride zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7-bis [o- (isobutyl) phenyl] -3,6-di-tert-fluorenyl] zirconium dichloride, dibenzyl methylene (cyclo 戊二烯基)[2,7- 二[邻(仲丁基)苯基]-3,6- 二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻(叔丁基)苯基]_3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻(正二十烷基)苯基]_3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二(邻环己基苯基)_3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二(联苯基-2-基)-3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻(2-萘基)苯基]_3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二[邻(2-菲基)苯基]_3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二(邻三甲基甲硅烷基苯基)_3,6-二叔丁基芴基]二氯化锆、二苄基亚甲基(环戊二烯基)[2,7-二(邻三苯基甲硅烷基苯基)-3,6-二叔丁基芴基]二氯化锆、二苯基亚甲基(环戊二烯 Pentadienyl) [2,7-bis [o- (sec-butyl) phenyl] -3,6-di-tert-fluorenyl] zirconium dichloride, dibenzylmethylene (cyclopentadienyl ) [2,7-bis [o- (tert-butyl) phenyl] _3,6- di-tert-fluorenyl] zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7 - bis [o- (n-eicosyl) phenyl] _3,6- di-tert-fluorenyl] zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7-di ( o-phenyl-cyclohexyl) _3,6- di-tert-fluorenyl] zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7-bis (biphenyl-2-yl) 3,6-di-t-butyl-fluorenyl] zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7-bis [o- (2-naphthyl) phenyl] _3,6 - di-tert-fluorenyl] zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7-bis [o- (2-phenanthryl) phenyl] _3,6- di-t fluorenyl-yl] zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7-bis (o-trimethylsilyl alkylphenyl) _3,6- di-tert-fluorenyl] zirconium dichloride, dibenzylmethylene (cyclopentadienyl) [2,7-bis (o-triphenylmethyl silyl alkylphenyl) -3,6-di-t-butyl-fluorenyl-yl] dichloride zirconium, diphenylmethylene (cyclopentadienyl )(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7- 二苯基-3,6- 二叔丁基芴基)二氯化锆、二苯基亚甲基(环戊二烯基)(2,7- 二对氯苯基-3,6- 二叔丁基芴基)二氯化锆、二对甲苯基亚甲基(环戊二烯基)(2,7- 二对氯苯基-3,6- 二叔丁基芴基)二氯化锆、二(对氯苯基)亚甲基(环戊二烯基)(2,7- 二对氯苯基-3,6- 二叔丁基芴基)二氯化锆、二(对三氟甲基苯基)亚甲基(环戊二烯基)(2,7-二对氯苯基-3,6-二叔丁基芴基)二氯化锆、二(2-萘基)亚甲基(环戊二烯基)(2,7-二对氯苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7- 二对氯苯基-3,6- 二叔丁基芴基)二氯化锆、二(对氯苄基)亚甲基(环戊二烯基)(2,7- 二对氯苯基-3,6- 二叔丁基芴基)二氯化锆、二(对甲基苄基)亚甲基(环戊二烯基)(2,7- 二对氯苯基-3,6- 二叔丁基芴基)二氯化锆 ) (2,7-diphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3, di-t-butyl-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-p-chlorophenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, di-p methylene (cyclopentadienyl) (2,7-p-chlorophenyl-3,6-di-tert-fluorenyl) zirconium dichloride, bis (p-chlorophenyl yl) methylene (cyclopentadienyl) (2,7-di-t-butyl-p-chlorophenyl-3,6-fluorenyl) zirconium dichloride, bis (p-trifluoromethylphenyl) alkylene methylene (cyclopentadienyl) (2,7-p-chlorophenyl-3,6-di-tert-fluorenyl) zirconium dichloride, bis (2-naphthyl) methylene (cyclopentadienyl- enyl) (2,7-di-t-butyl-p-chlorophenyl-3,6-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-two pairs chlorophenyl-3,6-di-tert-fluorenyl) zirconium dichloride, di (p-chlorobenzyl) methylene (cyclopentadienyl) (2,7-p-chlorophenyl-3, di-t-butyl-fluorenyl) zirconium dichloride, di (p-methylbenzyl) methylene (cyclopentadienyl) (2,7-di-t-butyl-3,6-dichlorobenzene for yl fluorenyl) zirconium dichloride 、二苄基亚甲基(环戊二烯基)(2,7- 二对氯苯基-3,6- 二.三甲基甲硅烷基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二对氯苯基-3,6-二枯基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二对氯苯基-3,6-金刚烷基芴基)二氯化锆、二甲基亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二乙基亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二正丙基亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二异丙基亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二正丁基亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二异丁基亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二仲丁基亚甲基(环戊二烯基 , Dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-p-chlorophenyl. Trimethyl silyl-fluorenyl) zirconium dichloride, dibenzylmethylene A yl (cyclopentadienyl) (2,7-p-chlorophenyl-3,6-dicumyl-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2, 7-p-chlorophenyl-3,6-adamantyl-fluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-p-trifluoromethylphenyl - 3,6-di-tert-fluorenyl) zirconium dichloride, diethyl methylene (cyclopentadienyl) (2,7-trifluoromethylphenyl-3,6-di-t yl fluorenyl) zirconium dichloride, di-n-propyl methylene (cyclopentadienyl) (2,7-trifluoromethylphenyl-3,6-di-tert-fluorenyl) dichloro zirconium, diisopropyl methyl (cyclopentadienyl) (2,7-trifluoromethylphenyl-3,6-di-tert-fluorenyl) zirconium dichloride, di-n-butyl methylene (cyclopentadienyl) (2,7-trifluoromethylphenyl-3,6-di-tert-fluorenyl) zirconium dichloride, di-iso-butyl methyl (cyclo pentadienyl) (2,7-trifluoromethylphenyl-3,6-di-tert-fluorenyl) zirconium dichloride, di-sec-methylenebis (cyclopentadienyl )(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二叔丁基亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二正辛基亚甲基(环戊二烯基)(2,7- 二对三氟甲基苯基-3,6- 二叔丁基芴基)二氯化锆、二-正三十烷基亚甲基(环戊二烯基)(2,7- 二对三氟甲基苯基-3,6- 二叔丁基芴基)二氯化锆、苯基亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二苯基亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二对甲苯基亚甲基(环戊二烯基)(2,7- 二对三氟甲基苯基-3,6- 二叔丁基芴基)二氯化锆、二(对氯苯基)亚甲基(环戊二烯基)(2,7- 二对三氟甲基苯基-3,6- 二叔丁基芴基)二氯化锆、二(对三氟甲基苯基)亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二(2-萘基)亚甲 ) (2,7-trifluoromethylphenyl-3,6-di-tert-fluorenyl) zirconium dichloride, di-t-butylmethylene (cyclopentadienyl) (2,7- two p-trifluoromethylphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride, di-n-octyl dimethyl (cyclopentadienyl) (2,7-p-trifluoromethyl phenyl 3,6-di-tert-fluorenyl) zirconium dichloride, di - n-triacontane methylene (cyclopentadienyl) (2,7-p-trifluoromethylphenyl - 3,6-di-tert-fluorenyl) zirconium dichloride, phenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-p-trifluoromethylphenyl-butyl fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-trifluoromethylphenyl-3,6-di-tert-fluorenyl) zirconium dichloride , di-p methylene (cyclopentadienyl) (2,7-trifluoromethylphenyl-3,6-di-tert-fluorenyl) zirconium dichloride, bis (p-chlorophenyl yl) methylene (cyclopentadienyl) (2,7-trifluoromethylphenyl-3,6-di-tert-fluorenyl) zirconium dichloride, bis (p-trifluoromethyl phenyl yl) methylene (cyclopentadienyl) (2,7-trifluoromethylphenyl-3,6-di-tert-fluorenyl) zirconium dichloride, bis (2-naphthyl) ethylene armor 基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二苄基亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆、二(对氯苄基)亚甲基(环戊二烯基)(2,7- 二对三氟甲基苯基-3,6- 二叔丁基芴基)二氯化锆、二(对甲基苄基)亚甲基(环戊二烯基)(2,7-二对三氟甲基苯基-3,6-二叔丁基芴基)二氯化锆和将上述化合物的锆原子取代为铪原子、钛原子的化合物或将上述化合物的氯原子取代为甲基、苄基的化合物或它们的组合等,但不局限于这些。 Yl (cyclopentadienyl) (2,7-trifluoromethylphenyl-3,6-di-tert-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl ) (2,7-trifluoromethylphenyl-3,6-di-tert-fluorenyl) zirconium dichloride, di (p-chlorobenzyl) methylene (cyclopentadienyl) (2 , 7-p-trifluoromethylphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride, bis () methylene (cyclopentadienyl p-methylbenzyl) (2,7 - di-p-trifluoromethylphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride, zirconium atom and the substituents for the above compounds is substituted with a hafnium atom, or a compound of titanium atom of chlorine atoms in the compound methyl, benzyl compound or a combination thereof, and the like, but not limited thereto. 另外,在铪原子、锆原子、钛原子中,优选为锆原子。 Further, a hafnium atom, a zirconium atom, a titanium atom, preferably zirconium atom. 上述化合物既可以单独使用,也可以组合2种以上使用。 Above compounds may be used alone or in combination of two or more thereof.

[0047] 过渡金属化合物(A)的制造方法 [0047] The transition metal compound (A) of the method of producing

[0048] 在本发明中所使用的过渡金属化合物(A)可以由公知的方法制造,制造方法没有特别限制。 [0048] In the present invention, used in the transition metal compound (A) can be produced by a known method, production method is not particularly limited. 作为制造方法,例如能够由日本特开2000-212194号公报、日本特开2004-168744号公报、日本特开2004-189666号公报、日本特开2004-161957号公报、日本特开2007-302854号公报、日本特开2007-302853号公报、W001/027124号公报、日本特表2001-526730号公报、日本特开平10-226694号公报等记载的方法制造。 As a manufacturing method, for example, Japanese Laid-Open Patent Publication No. 2000-212194, Japanese Patent Publication Laid-Open No. 2004-168744, Japanese Patent Publication Laid-Open No. 2004-189666, Japanese Patent Publication Laid-Open No. 2004-161957, Japanese Patent Laid-Open No. 2007-302854 method and Japanese Patent Publication Laid-open No. 2007-302853, W001 / Publication No. 027124, Japanese Unexamined Patent Publication No. 2001-526730, Japanese Unexamined Patent Publication No. 10-226694 and the like described in manufacturing.

[0049] 在烯烃聚合物的制造中供给过渡金属化合物(A)时的优选方式 [0049] The preferred embodiment is supplied when the transition metal compound (A) in the production of an olefin polymer

[0050] 接着,说明将本发明所使用的过渡金属化合物(A)作为烯烃聚合物的制造用催化剂(烯烃聚合催化剂)使用时的优选方式。 [0050] Next, description will be used in the present invention, the transition metal compound (A) as a catalyst for producing an olefin polymer (the olefin polymerization catalyst) used in the preferred embodiment the time.

[0051] <烯烃聚合催化剂> [0051] <olefin polymerization catalyst>

[0052] 将上述过渡金属化合物(A)作为烯烃聚合催化剂使用时,催化剂包含过渡金属化合物(A)和有机金属化合物(B )。 When [0052] the above-mentioned transition metal compound (A) as an olefin polymerization catalyst, the catalyst comprising a transition metal compound (A) and the organometallic compound (B). 其中,有机金属化合物(B )包含选自下述(b-1)、( b-2 )和(b-3)中的I种以上的有机金属化合物(B)。 Wherein, the organometallic compound (B) selected from the group comprising the following (b-1), the above (b-2), and (b-3) in the organic metal compound I (B).

[0053] (b-Ι)有机铝氧化合物 [0053] (b-Ι) an organoaluminum oxy-compound

[0054] (b-2)与上述过渡金属化合物(A)反应形成离子对的化合物 [0054] (b-2) ion pair with the aforementioned transition metal compound (A) to form

[0055] (b_3)有机铝化合物 [0055] (b_3) an organoaluminum compound

[0056] 其中,(b-1)、(b-2)和(b_3)既可以分别单独使用,也可以组合2种以上使用。 [0056] wherein, (b-1), (b-2) and (B_3) may be used alone, or two or more may be used in combination. 另外,烯烃聚合催化剂还可以根据需要包含颗粒状载体(C)、有机化合物成分(D)。 Further, the olefin polymerization catalyst may further comprise a particulate carrier (C) if necessary, the organic compound component (D). 以下,具体说明各成分。 Hereinafter, the respective components described in detail.

[0057][有机铝氧化合物(b-1)] [0057] [organoaluminum oxy-compound (b-1)]

[0058] 作为本发明中使用的有机铝氧化合物(b_l),可以直接使用现有公知的铝氧烷。 [0058] As the organoaluminum oxy-compound (B_L) used in the present invention, it can be used as conventionally known aluminoxane. 具体而言,能够列举下述通式[2]和/或下述通式[3]所代表的化合物, Specifically, can be exemplified by the following general formula [2] and / or the following formula [3] a compound represented by,

[0059] [0059]

Figure CN102686615BD00111

[0060](在上述通式[2]和[3]中,R表示碳原子数为I~10的烃基,η表示2以上的整数。),特别是R为甲基、η为3以上、优选为10以上的化合物适合作为甲基铝氧烷(MAO)利用。 [0060] (In the general formula [2] and [3], R represents a hydrocarbon group having a carbon number of I ~ 10, [eta] represents an integer of 2 or more.), In particular R is methyl, [eta] is 3 or more, preferably 10 or more of the compounds are suitable as methylaluminoxane (MAO) use. 在这些铝氧烷类中可以混入有机铝化合物。 In these aluminoxanes may be incorporated in the organoaluminum compound.

[0061]另外,作为在本发明中使用的有机铝氧化合物(b-Ι),也可以列举下述通式[4]那 [0061] Further, as the organoaluminum oxy-compound (b-Ι) used in the present invention may be exemplified by the following general formula [4] that

样的修饰甲基铝氧烷等。 Methyl aluminoxane other kind of modification.

[0062] [0062]

Figure CN102686615BD00121

[0063](其中,R表示碳原子数为2~10的烃基,m、η表示2以上的整数。) [0063] (wherein, R represents a hydrocarbon group having a carbon atom number of 2 to 10, m, η represents an integer of 2 or more.)

[0064] 该修饰甲基铝氧烷使用三甲基铝和三甲基铝以外的烷基铝配制。 [0064] This modified methyl aluminoxane alkyl aluminum other than trimethyl aluminum and trimethyl aluminum formulation. 这样的上述式 Such above-described formula

[4]的化合物一般称为ΜΜΑ0。 [4] The compound is generally called ΜΜΑ0. 这样的MMAO能够以在US4960878号和US5041584号中列举的方法配制。 MMAO can be formulated in such a method recited in number and number US5041584 US4960878. 另外,Tosoh-finechem公司等也将使用三甲基招和三异丁基招配制的、R为异丁基的化合物以MMAO或TMAO的名称进行商业生产。 Further, Tosoh-finechem companies will use the trimethyl strokes and strokes formulated triisobutyl, R is the isobutyl compound commercially produced under the name of MMAO or TMAO. 这些MMAO为改善了向各种溶剂的溶解性和保存稳定性的铝氧烷,具体而言,与上述式[2]、[3]那样的MAO不同,而是溶解于脂肪族烃或脂环族烃的铝氧烷。 The MMAO is aluminoxane improves the solubility in various solvents and storage stability, specifically, the above-mentioned formula [2], [3] of MAO as different, but dissolved in an aliphatic or alicyclic hydrocarbon aluminoxane aromatic hydrocarbon.

[0065] 作为在本发明中使用的有机铝氧化合物(b-Ι),也能够列举下述通式[5]所示的 [0065] As the organoaluminum oxy-compound (b-Ι) used in the present invention can be exemplified by the following general formula [5]

含硼有机铝氧化合物。 Boron-containing organoaluminum oxy-compound.

[0066] [0066]

Figure CN102686615BD00122

[0067](式中,Re表不碳原子数为I~10的径基。Rd相互相同或不同,表不氢原子、齒原子或碳原子数为I~10的烃基。) [0067] (wherein, Re is not a carbon atom number in Table I ~ yl .Rd 10 diameter same as or different from each other, the table is not a hydrogen atom, or a carbon atom teeth hydrocarbon group I ~ 10 in.)

[0068] 另外,在上述通式[2]~[5]中列举的有机铝氧化合物(b-ι)既可以单独使用,也可以混合2种以上使用。 [0068] Further, in the above general formula [2] to [5] include organoaluminum oxy-compound (b-ι) may be used alone, or two or more may be mixed and used.

[0069][与过渡金属化合物(A)反应形成离子对的化合物(b-2)] [0069] [transition metal compound (A) reaction of a compound of an ion pair (b-2) form]

[0070] 作为与过渡金属化合物(A)反应形成离子对的化合物(b-2)(以下有时略称为“离子性化合物”),能够列举在日本特开平1-501950号公报、日本特开平1-502036号公报、日本特开平3-179005号公报、日本特开平3-179006号公报、日本特开平3-207703号公报、日本特开平3-207704号公报、USP5321106号公报等中所记载的路易斯酸、离子性化合物、硼化合物和碳硼烷化合物等。 [0070] The compound with the transition metal compound (A) forming a reactive ion pair (b-2) (hereinafter sometimes abbreviated as "ionic compound"), can be exemplified in Japanese Unexamined Patent Publication No. 1-501950, Japanese Unexamined Patent Publication 1 Lewis Publication No. -502036, Japanese Unexamined Patent Publication No. 3-179005, Japanese Unexamined Patent Publication No. 3-179006, Japanese Patent Publication Laid-Open No. 3-207703, Japanese Unexamined Patent Publication No. 3-207704 Publication, USP5321106 Patent Publication No. like described in acid, an ionic compound, a boron compound and a carborane compound. 还能够列举杂多化合物和同多化合物。 They can also include heteropoly compounds and isopoly compounds.

[0071] 在本发明中,优选采用的离子性化合物(b-2)为下述通式[6]所示的硼酸盐化合物。 Borate compound [0071] In the present invention, the ionic compound (b-2) preferably employed is represented by general formula [6].

[0072] [0072]

Figure CN102686615BD00131

[0073](式中,作为Re+,可以列举H+、碳鎗阳离子、氧鎗阳离子、铵阳离子、鱗阳离子、环庚三烯基阳离子、具有过渡金属的二茂铁阳离子等。Rf~Ri相互相同或不同,为有机基,优选为芳基。) [0073] (wherein, as Re +, include H +, carbon gun cation, oxygen lance, an ammonium cation, scales cation, cycloheptatrienyl cation having a transition metal ferrocenium cation .Rf ~ Ri identical to each other or different, is an organic group, preferably an aryl group.)

[0074] 作为上述碳鎗阳离子,具体地可以列举三苯基碳鎗阳离子、三(甲基苯基)碳鎗阳离子、三(二甲基苯基)碳鎗阳离子等的三取代碳鎗阳离子等。

[0075] 作为上述铵阳离子,具体地可以列举三甲基铵阳离子、三乙基铵阳离子、三(正丙基)铵阳离子、三异丙基铵阳离子、三(正丁基)铵阳离子、三异丁基铵阳离子等的三烷基铵阳离子,N, N- 二甲基苯胺阳离子、N, N- 二乙基苯胺阳离子、N, N-2, 4,6-五甲基苯胺阳离子等的N,N- 二烷基苯胺阳离子、二异丙基铵阳离子、二环己基铵阳离子等的二烷基铵阳离 [0075] Examples of the ammonium cations, particularly cations include trimethyl ammonium, triethyl ammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, a tri异丁基铵阳离子等的三烷基铵阳离子,N, N- 二甲基苯胺阳离子、N, N- 二乙基苯胺阳离子、N, N-2, 4,6-五甲基苯胺阳离子等的N,N- 二烷基苯胺阳离子、二异丙基铵阳离子、二环己基铵阳离子等的二烷基铵阳离

罕坐丁寸ο

[0076] 作为上述鱗阳离子,具体地可以列举三苯基鱗阳离子、三(甲基苯基)鱗阳离子、三(二甲基苯基)鱗阳离子等的三芳基鱗阳离子等。

[0077] 上述之中,作为Re+,优选碳鎗阳离子、铵阳离子等,特别优选三苯基碳鎗阳离子、N, N- 二甲基苯胺阳离子、N, N- 二乙基苯胺阳离子。 [0077] Among the above, as Re +, preferably carbon gun, an ammonium cation and the like, particularly preferably triphenylcarbenium cation guns, N, N- dimethylanilinium cation, N, N- diethyl anilinium cation.

[0078] 作为碳鎗盐,具体地能够列举三苯基碳鎗四苯基硼酸盐、三苯基碳鎗四(五氟苯基)硼酸盐、三苯基碳鎗四(3,5-二.三氟甲基苯基)硼酸盐、三(4-甲基苯基)碳鎗四(五氟苯基)硼酸盐、三(3,5-二甲基苯基)碳鎗四(五氟苯基)硼酸盐等。 [0078] As the carbon gun salts, in particular can be guns include triphenylcarbenium tetraphenylborate, triphenylcarbenium gun tetrakis (pentafluorophenyl) borate, triphenylcarbenium gun tetrakis (3,5 - ditrifluoromethylphenyl) borate, tris (4-methylphenyl) carbonium gun tetrakis (pentafluorophenyl) borate, tris (3,5-dimethylphenyl) carbonium gun tetrakis (pentafluorophenyl) borate.

[0079] 作为铵盐,能够列举三烷基取代铵盐、N, N- 二烷基苯胺盐、二烷基铵盐等。 [0079] As the ammonium salt can include a trialkyl-substituted ammonium salts, N, N- dialkylanilinium salts, dialkylammonium salts and the like.

[0080] 作为三烷基取代铵盐,具体地例如可以列举三乙基四苯基硼酸铵、三丙基四苯基硼酸铵、三(正丁基)四苯基硼酸铵、三甲基四(对甲苯基)硼酸铵、三甲基四(邻甲苯基)硼酸铵、三(正丁基)四(五氟苯基)硼酸铵、三乙基四(五氟苯基)硼酸铵、三丙基四(五氟苯基)硼酸铵、三丙基四(2,4-二甲基苯基)硼酸铵、三(正丁基)四(3,5-二甲基苯基)硼酸铵、三(正丁基)四(4-三氟甲基苯基)硼酸铵、三(正丁基)四(3,5-二•三氟甲基苯基)硼酸铵、三(正丁基)四(邻甲苯基)硼酸铵、二.十八烷基甲基四苯基硼酸铵、二•十八烷基甲基四(对甲苯基)硼酸铵、二•十八烷基甲基四(邻甲苯基)硼酸铵、二.十八烷基甲基四(五氟苯基)硼酸铵、二.十八烷基甲基四(2,4-二甲基苯基)硼酸铵、二•十八烷基甲基四(3,5-二甲基苯基)硼酸铵、二•十八烷基甲基四(4-三氟甲基苯基)硼酸铵、二•十 [0080] As the trialkyl-substituted ammonium salts, particularly, for example, include triethyl ammonium tetraphenyl borate, tripropyl ammonium tetraphenyl borate, tri (n-butyl) ammonium tetraphenyl borate, trimethyl four (p-tolyl) borate, trimethyl ammonium tetraborate (o-tolyl), tri (n-butyl) ammonium tetraborate (pentafluorophenyl), triethyl ammonium tetraborate (pentafluorophenyl), tris propyl ammonium tetraborate (pentafluorophenyl), tripropyl tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) tetrakis (3,5-dimethylphenyl) borate, ammonium , tri (n-butyl) tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) (3,5-• trifluoromethylphenyl) borate, tri (n-butyl ) tetra (o-tolyl) borate, ammonium tetraphenyl borate two. octadecyl methyl, di octadecyl • tetrakis (p-tolyl) borate, di octadecyl • tetrakis (o-tolyl) borate, di. octadecyl ammonium borate, tetrakis (pentafluorophenyl), di. octadecyl tetrakis (2,4-dimethylphenyl) borate, di • stearyl tetrakis (3,5-dimethylphenyl) borate, di octadecyl • tetrakis (4-trifluoromethylphenyl) borate, bis • ten 八烷基甲基四(3,5-二•三氟甲基苯基)硼酸铵、二•十八烷基甲基铵 Tetrakis (3,5-trifluoromethylphenyl •) octadecyl ammonium borate, di • dioctadecylmethylammonium

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[0081] 作为N,N- 二烷基苯胺盐,具体地例如可以列举N,N- 二甲基苯胺四苯基硼酸盐、N,N-二甲基苯胺四(五氟苯基)硼酸盐、N,N-二甲基苯胺四(3,5-二•三氟甲基苯基)硼酸盐、N, N- 二乙基苯胺四苯基硼酸盐、N, N- 二乙基苯胺四(五氟苯基)硼酸盐、N, N- 二乙基苯胺四(3,5- 二.三氟甲基苯基)硼酸盐、N, N-2, 4,6-五甲基苯胺四苯基硼酸盐、N,N-2,4,6-五甲基苯胺四(五氟苯基)硼酸盐等。 [0081] As the N, N- dialkylanilinium salts, can include specifically, for example N, N- dimethylanilinium tetraphenylborate, N, N- dimethylanilinium tetrakis (pentafluorophenyl) boron salt, N, N- dimethylanilinium tetrakis (• 3,5-trifluoromethylphenyl) borate, N, N- diethylanilinium tetraphenylborate, N, N- two diethylanilinium tetrakis (pentafluorophenyl) borate, N, N- diethylaniline (3,5-.-trifluoromethylphenyl) borate, N, N-2, 4,6 - pentamethylanilinium tetraphenylborate, N, N-2,4,6- pentamethylanilinium tetrakis (pentafluorophenyl) borate.

[0082] 作为二烷基铵盐,具体地例如可以列举二(1-丙基)四(五氟苯基)硼酸铵、二环己基四苯基硼酸铵等。 [0082] As the dialkylammonium salts, may be mentioned specifically, for example bis (1-propyl) tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate ammonium group.

[0083] 其它,也可以无限制地使用由本申请人公开的离子性化合物(日本特开2004-51676 号公报)。 [0083] Other, it may be used without limitation ionic compound (Japanese Patent Laid-Open Publication No. 2004-51676) disclosed by the present applicant.

[0084] 另外,上述那样的离子性化合物(b-2)既可以单独使用,也可以混合2种以上使用。 [0084] Further, as the ionic compound (b-2) may be used alone, or two or more may be mixed and used.

[0085][有机铝化合物(b_3)] [0085] [organoaluminum compound (B_3)]

[0086] 作为形成烯烃聚合催化剂的有机铝化合物(b_3),例如能够列举下述通式[7]所示的有机铝化合物、下述通式[8]所示的第I族金属与铝的络合烷基化物等。 The organic aluminum compound [0086] As the organic aluminum compound (B_3) forming the olefin polymerization catalyst, for example, include the following general formula [7], the following general formula [8] as shown in Group I metal and aluminum complex alkylate and the like.

[0087] RamAl(ORb)nHpXq……[7] [0087] RamAl (ORb) nHpXq ...... [7]

[0088](式中,1^和Rb 相互相同或不同,表不碳原子数为I~15的烃基,优选表不碳原子数为I~4的烃基,X表示1¾原子,m为O < m ≤3的数,η为O ≤ η < 3的数,ρ为O≤ρ< 3的数,q为O≤q < 3的数,且m+n+p+q = 3。)所示的有机招化合物。 [0088] (wherein, 1 ^ and Rb are the same or different, the table is not a carbon number hydrocarbon group I ~ 15, and preferably the table is not a carbon number hydrocarbon group I ~ 4, X is 1¾ atoms, m is O < number m ≤3, and [eta] is O ≤ η <number 3, [rho] is O≤ρ <number 3, q ​​is an O≤q <number 3, and m + n + p + q = 3.) shown organic compounds strokes.

[0089] 作为这样的化合物的具体例子,能够列举三甲基铝、三乙基铝、三(正丁基)铝、三(正己基)招、二(正羊基)招等的二(正烷基)招;二异丙基招、二异丁基招、二仲丁基招、三叔丁基铝、三(2-甲基丁基)铝、三(3-甲基己基)铝、三(2-乙基己基)铝等的三(支链烷基)招;二环己基招、二环羊基招等的二环烷基招;二苯基招、二甲苯基招等的二芳基铝;二异丙基氢化铝、二异丁基氢化铝等的二烷基氢化铝;通式(1-C4H9)xAly(C5Hltl)z (式中,x、y、z为正数,z ≤ 2x。)所示的异戊烯基铝等的烯基铝;异丁基铝甲醇盐、异丁基铝乙醇盐等的烷基招醇盐;二甲基招甲醇盐、二乙基招乙醇盐、二丁基招丁醇盐等的二烷基招醇盐;乙基铝倍半乙醇盐、丁基铝倍半丁醇盐等的烷基铝倍半醇盐;具有通式Ra2.5A1 (ORb)a5等所示的平均组成的部分烷氧基化的烷基铝;二乙基铝酚盐、二乙 [0089] Specific examples of such compounds can include trimethylaluminum, triethylaluminum, tri (n-butyl) aluminum, tri (n-hexyl) move, di (n-sheep-yl) move like di (n alkyl) move; diisopropyl strokes, strokes diisobutyl, di-sec strokes, tri-butyl aluminum, tri (2-methylbutyl) aluminum, tri (3-methylhexyl) aluminum, tris (2-ethylhexyl) aluminum, tris (branched alkyl) move; dicyclohexyl strokes, strokes bicyclic group such as sheep move bicyclic alkyl; diphenyl strokes, strokes and the like xylyl di aryl aluminum; diisopropyl aluminum hydride, diisobutyl aluminum hydride, dialkylaluminum hydride and the like; formula (1-C4H9) xAly (C5Hltl) z (wherein, x, y, z are positive numbers, . z ≤ 2x) shown isopentenyl alkenyl aluminum such as aluminum; isobutylaluminum methoxide, isobutylaluminum ethoxide and the like move alkyl alkoxides; dimethyl strokes methoxide, diethyl move ethoxide, dibutyl dialkyl strokes strokes butoxide alkoxide salt and the like; the alkyl ethoxide ethylaluminum sesquichloride, butylaluminum sesquichloride butoxide aluminum sesquichloride alkoxide; Ra2 have the general formula alkylaluminum having an average composition of the partially alkoxylated .5A1 (ORb) a5 shown like; diethyl aluminum phenoxide, diethyl 基铝(2,6-二叔丁基-4-甲基酚盐)等的烷基招芳族酿;二甲基氣化招、二乙基氣化招、二丁基氣化招、二乙基漠化招、二异丁基氯化铝等的二烷基卤化铝;乙基倍半氯化铝、丁基倍半氯化铝、乙基倍半溴化铝等的烷基倍半卤化铝;乙基二氯化铝等的烷基二卤化铝等部分卤化的烷基铝;二乙基氢化铝、二异丁基氢化铝等的二烷基氢化铝;乙基二氢化铝、丙基二氢化铝等的烷基二氢化铝等其他部分氣化的烷基招;乙氧基氣化乙基招、丁氧基氣化丁基招、乙氧基漠化乙基招等部分烧氧基化和卤化的烷基铝等。 Aluminum-yl (2,6-di-t-butyl-4-methylphenol salt) and the like stuffed alkyl aromatic strokes; dimethyl strokes gasification, gasification strokes diethyl, dibutyl gasification strokes, di- dialkylaluminum halides ethyl desertification strokes, diisobutylaluminum chloride and the like; ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethylaluminum sesquichloride alkyl bromide such sesqui dialkyl aluminum hydride, diethyl aluminum hydride, diisobutyl aluminum hydride and the like;; aluminum halide; partially halogenated alkyl aluminum such as diethyl aluminum chloride, alkyl halide, diethyl aluminum hydride, the alkyl portions of the other strokes vaporized propyl aluminum dialkyl hydride such as aluminum hydride and the like; ethoxy ethyl move gasification, gasification of butyl butoxy strokes, strokes and the like ethoxylated ethyl desertification portion burning aluminum alkyl halide group and the like.

[0090] M2AlRa4......[8] [0090] M2AlRa4 ...... [8]

[0091](式中,M2表示L1、Na或K,Ra表示碳原子数为I~15的烃基,优选表示碳原子数为I~4的烃基。)所示的元素周期表第I族金属与铝的络合烷基化物。 [0091] (wherein, M2 represents L1, Na or K, Ra represents a hydrocarbon group having carbon atoms of I ~ 15, and preferably represents a hydrocarbon group having a carbon number of I ~. 4.) As shown in the Periodic Table Group I metal the aluminum complex alkylate.

[0092] 作为这样的化合物的具体例子,可以列举LiAl (C2H5)4, LiAl (C7H15)4等。 [0092] Specific examples of such compounds include LiAl (C2H5) 4, LiAl (C7H15) 4 and the like.

[0093] 另外,也能够使用与上述通式[8]所示的化合物类似的化合物,例如,能够列举2个以上的铝化合物经由氮原子结合的有机铝化合物。 [0093] Further, similar to the compounds represented by the general formula [8] can also be used, for example, can be exemplified organoaluminum compound having two or more aluminum compounds bonded via a nitrogen atom. 作为这样的化合物,具体地能够列举(C2H5)2AlN(C2H5)Al (C2H5)2 等。 As such a compound, capable of specifically include (C2H5) 2AlN (C2H5) Al (C2H5) 2 and the like.

[0094] 从获得容易性方面出发,作为有机铝化合物(b_3),优选使用三乙基铝、三异丁基 [0094] From the aspect of easy availability, as an organoaluminum compound (B_3), preferably triethyl aluminum, triisobutyl

铝、三(正辛基)铝、二异丁基氢化铝。 Aluminum, tri (n-octyl) aluminum, diisobutyl aluminum hydride. [0095] 另外,上述那样的有机铝化合物(b_3)既可以单独使用,也可以混合2种以上使用。 [0095] Further, the above-described organoaluminum compound (B_3) may be used alone, or two or more may be mixed and used.

[0096] 另外,在本发明中使用的烯烃聚合催化剂,除过渡金属化合物(A)和有机金属化合物(B)以外,根据需要还可以包含载体(C)。 [0096] The olefin used in the present invention, the polymerization catalyst, in addition to the transition metal compound (A) and the organometallic compound (B), if necessary may further comprise a carrier (C).

[0097][载体(C)] [0097] [carrier (C)]

[0098] 本发明中使用的载体(C )为无机或有机的化合物,是颗粒状或微粒状固体。 [0098] The carrier used in the present invention (C) is an inorganic or organic compounds, granular or fine particulate solid. 其中,作为无机化合物,优选多孔氧化物、无机氯化物、粘土、粘土矿物或离子交换性层状化合物 Wherein, as the inorganic compound is preferably porous oxides, inorganic chlorides, clay, clay mineral or ion-exchangeable layered compound

[0099] 作为多孔氧化物,具体而言能够使用Si02、A1203、MgO, ZrO, TiO2, B203、CaO, ZnO,BaO, ThO2等或包含它们的复合物或者混合物。 [0099] As the porous oxide, specifically, can be used Si02, A1203, MgO, ZrO, TiO2, B203, CaO, ZnO, BaO, ThO2 and the like or a composite or a mixture thereof. 例如,能够使用天然或合成沸石、SiO2-MgO,SiO2-Al2O3^ SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3^ SiO2-TiO2-MgO 等。 For example, it is possible to use natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3 ^ SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3 ^ SiO2-TiO2-MgO and the like. 其中,优选以SiO2 和/ 或Al2O3为主要成分的多孔氧化物。 Wherein, preferably of SiO2 and / or Al2O3 as a main component of the porous oxide. 这样的多孔氧化物,其性状随着种类和制法而不同,在本发明中优选使用的载体,粒径为10~300 μ m,优选为20~200 μ m,比表面积在50~1000m2/g的范围,优选在100~700m2/g的范围,细孔容积希望在0.3~3.0cmVg的范围。 Such porous oxide, depending on the kind and physical properties and manufactured by different methods, in the present invention, the carrier preferably used in a particle size of 10 ~ 300 μ m, preferably 20 ~ 200 μ m, specific surface area of ​​50 ~ 1000m2 / g and preferably in the range 100 ~ 700m2 / g, pore volume in the desired range of 0.3 ~ 3.0cmVg. 这样的载体,根据需要在100~1000°C烧制使用,优选在150~700°C烧制使用。 Such vectors, as necessary fired 100 ~ 1000 ° C, preferably in in 150 ~ 700 ° C firing.

[0100] 作为无机氯化物,可以使用MgCl2、MgBr2、MnCl2、MnBr2等。 [0100] Examples of the inorganic chlorides can be used MgCl2, MgBr2, MnCl2, MnBr2 and the like. 无机氯化物既可以直接使用,也可以由球磨机、振动磨粉碎后使用。 The inorganic chlorides may be used directly, or may be composed of a ball mill, a vibration mill pulverization after use. 另外,也可以使用使无机氯化物溶解在醇等的溶剂中后、由析出剂使其以微粒状析出的析出物。 Further, the inorganic chloride may be used dissolved in a solvent such as alcohol, from the precipitating agent so as to precipitate particulate precipitated.

[0101] 在本发明中使用的粘土,通常以粘土矿物为主要成分构成。 另外,在本发明中使用的离子交换性层状化合物,是具有由离子键等构成的面相互以弱结合力平行重叠而成的晶体结构的化合物,含有的离子可以交换。 Further, ion-exchange layered compound used in the present invention is a compound having a weak bonding force in parallel with each other by superimposing surface constituted by ionic bond or the like crystal structure, ions contained can be exchanged.大部分粘土矿物为离子交换性层状化合物。另外,作为这些粘土、粘土矿物、离子交换性层状化合物,不限于天然产物,也能够使用人工合成物。 另外,作为粘土、粘土矿物或离子交换性层状化合物,可以列举粘土、粘土矿物或六方紧密堆积型、锑型、CdCl2型、CdI2型等具有层状晶体结构的离子结晶性化合物等。 Further, as a clay, clay mineral or ion-exchangeable layered compound include ionic crystalline compounds having a layered crystal structure of the clay, clay mineral or a hexagonal close-packed type, antimony type, type of CdCl2, CdI2 type and the like. 作为这样的粘土、粘土矿物,可以列举高岭土、膨润土、木节粘土、蛙目粘土、水铝英石、水硅铁石、叶蜡石、云母类、蒙脱石类、蛭石、绿泥石类、坡缕石、高岭石、珍珠陶土、地开石、埃洛石等,作为离子交换性层状化合物,可以列举α -Zr (HAsO4)2.Η20、α -Zr (HPO4) 2、α -Zr (KPO4)2.3Η20、α -Ti (HPO4)2, α -Ti (HAsO4)2.H2O, α-Sn (HPO4) 2.H2O、y -Zr (HPO4)2, y -Ti (HPO4)2,Y-Ti(NH4PO4)2.H2O等多价金属的结晶性酸性盐等。 Examples of such clay, clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite water, pyrophyllite, mica group, montmorillonite group, vermiculite, chlorite group 、坡缕石、高岭石、珍珠陶土、地开石、埃洛石等,作为离子交换性层状化合物,可以列举α -Zr (HAsO4)2.Η20、α -Zr (HPO4) 2、α -Zr (KPO4)2.3Η20、α -Ti (HPO4)2, α -Ti (HAsO4)2.H2O, α-Sn (HPO4) 2.H2O、y -Zr (HPO4)2, y -Ti (HPO4) 2,Y-Ti(NH4PO4)2.H2O等多价金属的结晶性酸性盐等。也优选对本发明中使用的粘土、粘土矿物施加化学处理。作为化学处理,能够使用除去在表面附着的杂质的表面处理、给粘土的晶体结构造成影响的处理等。作为化学处理,具体地可以列举酸处理、碱处理、盐类处理、有机物处理等。

[0102]在本发明中使用的离子交换性层状化合物可以是利用离子交换性,通过将层间的交换性离子与其他体积大的离子交换而层间扩大的状态的层状化合物。 Ion-exchange layered compound used in the present invention [0102] may be the use of ion-exchangeable, layered compound by the ion-exchangeable interlayer between layers enlarged condition with other bulky ion exchange. 这样的体积大的离子承担支持层状结构的支柱的作用,通常称为柱状物(Pillar)。 Such bulky ions to assume the role of supporting the layered structure of the strut, commonly referred to as pillar (Pillar). 另外,将这样在层状化合物的层间导入其他物质称为嵌入。 Furthermore, introducing other substances referred thus embedded between layers of the layered compound. 作为嵌入的客体化合物,可以列举TiCl4、ZrCl4等阳离子性无机化合物,Ti (OR)4、Zr (OR)4、PO (OR) 3> B (OR) 3等金属烷氧化物(R为烃基等),[Al13O4(OH)24] 7+、[Zr4(OH)14] 2+、[Fe3O(OCOCH3)6] +等的金属氢氧化物离子。 As an embedded object compounds include TiCl4, ZrCl4, etc. cationic inorganic compound, Ti (OR) 4, Zr (OR) 4, PO (OR) 3> B (OR) 3 a metal alkoxide (R is a hydrocarbon group, etc. metallic hydroxide ions), [Al13O4 (OH) 24] 7 +, [Zr4 (OH) 14] 2 +, [Fe3O (OCOCH3) 6] + or the like. 这些化合物可以单独或组合2种以上使用。 These compounds may be used alone or in combination of two or more. 另外,在嵌入这些化合物时,也能够使水解Si (OR) 4、A1 (0R)3、Ge(OR)4等的金属烷氧化物(R为烃基等)得到的聚合物、SiO2等胶体状无机化合物共存。 Further, when embedding these compounds, it is possible to make the hydrolyzed Si (OR) 4, A1 (0R) 3, Ge (OR) 4 such as a metal alkoxide (R is a hydrocarbon group, etc.) to give a polymer, SiO2, etc. colloidal The inorganic compound to coexist. 另外,作为柱状物,可以列举在层间嵌入上述金属氢氧化物离子后由加热脱水生成的氧化物等。 Further, the pillars include oxides embedded in the above-mentioned metallic hydroxide ions generated by the thermal dehydration of the interlayer and the like. 其中,优选为粘土或粘土矿物,特别优选为蒙脱石、蛭石、针钠钙石、带云母和合成云母。 Wherein, preferably a clay or clay minerals, and particularly preferably montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica.

[0103] 作为载体(C)的有机化合物,能够列举粒径在10~300 μ m范围的颗粒状或微粒状固体。 [0103] As the organic compound carrier (C) can be exemplified in a particle size range of 10 ~ 300 μ m of granular or fine particulate solid. 具体地可以列举以乙烯、丙烯、1-丁烯、4-甲基-1-戊烯等碳原子数为2~14的α -烯烃作为主要成分所生成的(共聚)聚合物,以乙烯基环己烷、苯乙烯为主要成分所生成的(共聚)聚合物、和它们的改性物。 In particular it may be mentioned ethylene, propylene, 1-butene, 4-methyl-1-pentene carbon atoms of α 2 ~ 14 - olefin as a main component generated by the (co) polymers, vinyl cyclohexane, styrene as a principal component of the resulting (co) polymers, and modifications thereof.

[0104] 另外,上述那样的载体(C)既可以单独使用,也可以混合2种以上使用。 [0104] Further, the above-described carrier (C) may be used alone, or two or more may be mixed and used.

[0105] 另外,在本发明中使用的烯烃聚合催化剂,除过渡金属化合物(Α)、有机金属化合物成分(B)和根据需要使用的载体(C)以外,还可以包含有机化合物(D)。 [0105] The olefin used in the present invention, the polymerization catalyst in addition to the transition metal compound ([alpha]), the organometallic compound component (B) and according to need to use a carrier other than (C), may further comprise an organic compound (D).

[0106][有机化合物(D)] [0106] [organic compound (D)]

[0107] 在本发明中使用的有机化合物(D),根据需要,出于使聚合性能和生成的聚合物的物性提高的目的而使用。 [0107] organic compound (D) used in the present invention, if necessary, for the purpose of improving physical properties of the polymerization and the resulting properties of the polymer used. 作为这样的有机化合物,可以列举醇类、酚性化合物、羧酸、磷化合物和磺酸盐等,但不限于此。 Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates, but not limited thereto.

[0108] 另外,上述那样的有机化合物(D )既可以单独使用,也可以混合2种以上使用。 [0108] Further, the above-described organic compound (D) may be used alone, or two or more may be mixed and used.

[0109] 在聚合时,上述成分的使用方法、添加顺序任意选择,可以列举如下的方法。 [0109] In the polymerization, a method using the above components, order of addition arbitrarily selected, the following method can be exemplified.

[0110] (I)在聚合器中单独添加过渡金属化合物(A)的方法。 The method of the transition metal compound (A), [0110] (I) added alone to the polymerization reactor.

[0111] (2)在聚合器中以任意顺序添加过渡金属化合物(A)和有机金属化合物(B)的方法。 [0111] (2) method of adding the transition metal compound (A) and the organometallic compound (B) in any order to the polymerization reactor.

[0112] (3)在聚合器中以任意顺序添加在载体(C)上载持有过渡金属化合物(A)的催化剂成分、有机金属化合物(B)的方法。 [0112] (3) in a polymerization reactor in any order added to the carrier (C) a transition metal catalyst component-carrying compound (A) of an organic metal compound (B) is.

[0113] (4)在聚合器中以任意顺序添加在载体(C)上载持有有机金属化合物(B)的催化剂成分、过渡金属化合物(A)的方法。 [0113] (4) in a polymerization reactor in any order added to the carrier (C) an organometallic catalyst component-carrying compound (B), and a metal compound (A) transition.

[0114] (5)在聚合器中添加在载体(C)上载持有过渡金属化合物(A)和有机金属化合物(B)的催化剂成分的方法。 [0114] (5) was added to the polymerization reactor on a carrier (C) of the method of the transition metal compound catalyst component (A) and the organometallic compound (B) is held by the carrier.

[0115] 在上述(I)~(5)的方法中,有机化合物(D)可以以任意顺序在聚合器中添加,另外,也可以事先使其与(A)~(C)中的至少I种以上成分预先接触以后在聚合器中添加。 [0115] In the method (I) ~ (5) above, the organic compound (D) may be added to the polymerization reactor in any order. In addition, it may be previously reacted with (A) ~ (C) at least I after the above components were previously contacted species added to the polymerization reactor. 另外,在上述(2)~(5)的方法中,催化剂成分的至少2种以上可以预先接触。 In the method (2) to (5) above, or two or more may be previously in contact with at least a catalyst component.

[0116] 在载持有机金属化合物(B)的上述(4)、(5)的方法中,根据需要,也可以以任意顺序添加未被载持的有机金属化合物(B)。 [0116] In the method (4), (5) the above-carrying metal compound (B) is, if necessary, may be added not supported organometallic compound (B) in any order. 此时,有机金属化合物(B)既可以相同也可以不同。 In this case, the organometallic compound (B) may be the same or different.

[0117] 另外,在成分(C)上载持有过渡金属化合物(A)的固体催化剂成分、在成分(C)上载持有过渡金属化合物(A)和有机金属化合物(B)的固体催化剂成分,既可以预聚合烯烃,也可以在被预聚合的固体催化剂成分上再载持催化剂成分。 [0117] Further, in the component (C)-carrying solid catalyst component of the transition metal compound (A) in the component (C)-carrying solid catalyst component a transition metal compound (A) and the organometallic compound (B), and an olefin may be prepolymerized, and then may be supported on the solid catalyst component being prepolymerized catalyst component.

[0118] 在本发明的烯烃聚合物的制造方法中,在上述那样的烯烃聚合用催化剂的存在下,通过聚合碳原子数为3~10的α-烯烃与乙烯而得到α-烯烃聚合物。 [0118] In the method for producing an olefin polymer according to the present invention, with the presence of a catalyst, by polymerizing carbon atoms α- olefin and 3 to 10 ethylene α- olefin polymer obtained in the above-described olefin polymerization.

[0119] < α-烯烃〉 [0119] <α- olefins>

[0120] 可以在本发明中使用的碳原子数为3~10的α -烯烃,例如,能够列举丙烯、1_ 丁稀、1_戍稀、1_己稀、1_庚稀、1_羊稀、1_壬稀、1_癸稀、3-甲基_1-丁稀、3_甲基_1-戍烯、4-甲基-1-戊烯、3-乙基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、4,4-二甲基_1_戍烯、4-乙基-1-己烯、3-乙基-1-己烯等。 [0120] The number of carbon atoms can be used in the present invention is the α 3 ~ 10 - olefin, for example, can be cited propylene, but-1_ dilute, dilute Shu 1_, 1_ hexene, heptene 1_, 1_ sheep dilute, dilute 1_ nonyl, decyl dilute 1_, 3-methyl-butoxy _1- dilute, 3_ _1- methyl pentene, 4-methyl-1-pentene, 3-ethyl-pentyl hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl _1_ pentene, 4-ethyl-1-hexene, 3 ethyl-1-hexene. 其中,优选碳原子数为3~8的α-烯烃,更优选碳原子数为3~6的α -烯烃,特别优选为丙烯、1-丁烯、1-己烯、4-甲基-1-戊烯。 Wherein the number of carbon atoms is preferably α- olefins having 3 to 8, more preferably carbon atoms of α 3 ~ 6 - olefins, more preferably propylene, 1-butene, 1-hexene, 4-methyl-1 - pentene.

[0121] 另外,这些碳原子数为3~10的α -烯烃能够单独使用I种或组合2种以上使用。 [0121] Further, the number of carbon atoms of α 3 ~ 10 - I-olefins may be used alone or in combination of two or more. 关于α-烯烃的选择,可以适当选择以使生成的聚合物特性上达到最优。 On selecting α- olefin may be suitably selected so that the optimal characteristics of the resulting polymer. 作为选择的I个例子,为使硫化处理该聚合物或包含该聚合物的混合物时的物性达到期望值等。 As an example I selected, such that when the physical properties of the vulcanized polymer or polymer mixture comprising the desired value and the like.

[0122] <烯烃聚合物的制造方法> [0122] <Method for producing an olefin polymer>

[0123] 本发明也可以按照溶液聚合、悬浮聚合等的液相聚合法或气相聚合法中的任意I种方法实施。 [0123] The present invention may be any phase polymerization or gas phase polymerization method I species was embodied in a method of solution polymerization, suspension polymerization and the like.

[0124] 作为在液相聚合法中使用的惰性烃介质(惰性烃溶剂),具体地能够列举丙烷、丁烷、戊烷、己烷、庚烷、辛烷、癸烷、十二碳烷、氯化乙烯、二氯甲烷、煤油等的脂肪族烃;环戊烷、环己烷、甲基环戊烷等的脂环式烃;苯、甲苯、氯苯、二甲苯等的芳香族烃;或者它们的混合物。 [0124] As the inert hydrocarbon medium (inert hydrocarbon solvent) used in the liquid phase polymerization, capable of specifically include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, ethylene chloride, methylene chloride, aliphatic hydrocarbons such as kerosene; cyclopentane, cyclohexane, methylcyclopentane and the like alicyclic hydrocarbons; benzene, toluene, chlorobenzene, xylene or the like aromatic hydrocarbons; or mixtures thereof. 另外,也能够将α-烯烃本身作为溶剂使用。 Further, it is possible to α- olefin itself as a solvent.

[0125] 使用上述那样的烯烃聚合用催化剂,在进行烯烃的聚合时,每I升反应容积,过渡金属化合物(A)通常以10_9~10—1摩尔、优选以10_8~10_2摩尔的量使用。 [0125] Using the above-described olefin polymerization catalyst during the polymerization of olefins, per I liter of the reaction volume, the transition metal compound (A) is typically ~ 10-1 mol 10_9, 10_8 ~ 10_2 preferably used equimolar amounts.

[0126] 有机铝氧化合物(b-Ι)以与过渡金属化合物(A)中的全部过渡金属原子(M)的摩尔比[(bl)/M]通常为0.01 ~ 50000、优选为0.05~2000的量使用。 [0126] The organoaluminum oxy-compound (b-Ι) to the transition metal compound to all the transition metal atom (A), (M) in a molar ratio of [(bl) / M] is usually 0.01 to 50,000, preferably from 0.05 to 2000 the amount of use. 离子性化合物(b_2)以离子性化合物(b-2)与过渡金属化合物(A)中的过渡金属原子(M)的摩尔比[(b-2)/M]通常为0.01~50000、优选为0.05~2000的量使用。 Ionic compound (B_2) to the ionic compound (b-2) the transition metal compound (A) to the transition metal atom (M) in a molar ratio [(b-2) / M] is usually 0.01 to 50,000, preferably 0.05 to 2,000. 有机铝化合物(b_3)以有机铝化合物(b-3)中的铝原子与过渡金属化合物(A)中的全部过渡金属(M)的摩尔比[(b-3)/M]通常为0.01~5000、优选为0.05~2000的量使用。 The organic aluminum compound (B_3) an organic aluminum compound (b-3) of the aluminum atom to the transition metal compound (A) in all the transition metal (M) molar ratio [(b-3) / M] is usually 0.01 to 5000, preferably 0.05 to 2,000.

[0127] 另外,使用这样的烯烃聚合催化剂的烯烃的聚合温度通常为+25~+200°C,优选为+25~+170°C的范围,更优选为+30~+150°C的范围。 [0127] Further, the use of such olefin polymerization catalyst for olefin polymerization temperature is usually + 25 ~ + 200 ° C, preferably a range of + 25 ~ + 170 ° C, more preferably of + 30 ~ + 150 ° C range . 根据得到的α-烯烃聚合物的分子量、烯烃聚合催化剂的聚合活性而定,但从生产率的观点出发,优选为+30°C以上。 The molecular weight of the α- olefin polymer obtained, the polymerization activity of the catalyst for olefin polymerization may be, but from the viewpoint of productivity, is preferably less than + 30 ° C.

[0128] 聚合压力通常是在常压~IOMPa表压、优选在常压~5MPa表压的条件下,聚合反应能够以间歇式、半连续式、连续式中的任意I种方法进行。 [0128] The polymerization pressure is generally atmospheric pressure ~ IOMPa gauge pressure, preferably at normal pressure ~ 5MPa gauge pressure, the polymerization reactor can be a batch, semi-continuous, continuous method of any of Formula I are carried out. 还可以将聚合分为反应条件不同的2阶段以上进行。 The polymerization may also be divided into two or more stages under different reaction conditions were.

[0129] 得到的烯烃聚合物的分子量也能够通过使氢在聚合系统内存在,或使聚合温度变化来调节。 [0129] molecular weight of the olefin polymer obtained can also be adjusted by allowing hydrogen to exist in the polymerization system or changing the polymerization temperature. 添加氢时,其量优选为每Ikg烯烃0.001~100NL左右。 When hydrogen is added, preferably in an amount of about Ikg olefin per 0.001 ~ 100NL. 另外,也能够由使用的成分(B)的量来调节。 Further, it is possible to adjust the amount of the component (B) is used. 此时,成分(B)具体地可以列举三异丁基铝、甲基铝氧烷、二乙基锌 In this case, component (B). Specific examples include triisobutylaluminum, methylaluminoxane, diethyl zinc

坐寸ο Sit inch ο

[0130] 在本发明的烯烃聚合物的制造方法中,其特征在于,将聚合反应系统中的乙烯供给量限制在某规定量,如下进行确定。 [0130] In the method for producing an olefin polymer according to the present invention, wherein the supply amount of the polymerization of ethylene in the reaction system are limited to a predetermined amount, determined as follows. 首先,在将碳原子数为3~10的α -烯烃作为气体供给时,乙烯和碳原子数为3~10的α -烯烃既可以在聚合器中分别连续供给,也可以间歇地供给。 First, the number of carbon atoms of α 3 ~ 10 - olefin as a gas supply, and the ethylene carbon atoms of α 3 ~ 10 - olefins may be separately fed to the polymerization reactor continuously or intermittently supplied. 另外,将供给聚合器的乙烯的摩尔数设为Pe,将碳原子数为3~10的α -烯烃的摩尔数设为匕时,由于乙烯供给量微小以供给的乙烯全部溶解于液体为前提,规定液体中的摩尔分数PeAV此时,以0.001 ( ΡΕ/Ρ0 ( 0.030为特征,如果为该范围,就能够任意使用,但优选为0.001 ^ ΡΕ/Ρ0 ( 0.020,更优选为0.001 ^ ΡΕ/Ρ0 ( 0.010,最优选为0.001 ^ Pe/P0 ^ 0.005ο[0131] 另一方面,将碳原子数为3~10的α -烯烃作为液体供给时,将供给聚合器的乙烯的摩尔数设为Pe,将碳原子数为3~10的α-烯烃的摩尔数设为匕时,以供给的乙烯溶解于碳原子数为3~10的α -烯烃为前提,规定液体中的摩尔分数PeAV此时,以0.001 ^Pe/P0 ( 0.030为特征,如果为该范围,就能够任意使用,但优选为0.001 ( ΡΕ/Ρ0 ( 0.020,更优选为0.001 ^ ΡΕ/Ρ0 ( 0.010,最优选为0.001 ^ ΡΕ/Ρ0 ( 0.005。 Further, the number of moles of ethylene fed to the polymerization reactor Pe, the number of carbon atoms of 3 to 10 α - olefin to the number of moles of dagger, since the slight amount of ethylene supplied to all ethylene feed is dissolved in the liquid as a precondition , a predetermined liquid mole fraction PeAV at this time, 0.001 (ΡΕ / Ρ0 (0.030 is characterized, if this range, it is possible to use an arbitrary, but is preferably 0.001 ^ ΡΕ / Ρ0 (0.020, more preferably 0.001 ^ ΡΕ / Ρ0 (0.010, most preferably 0.001 ^ Pe / P0 ^ 0.005ο [0131] On the other hand, the number of carbon atoms of α 3 ~ 10 - the number of moles of olefin fed as a liquid, the supply of ethylene to the polymerization reactor PE, when the molar number of carbon atoms, α- olefins having 3 to 10 set dagger, a supply of ethylene was dissolved in 3 carbon atoms to 10 [alpha] - olefin is provided, in predetermined molar fraction of this liquid PeAV when to 0.001 ^ Pe / P0 (0.030 is characterized, if this range, it is possible to use an arbitrary, but is preferably 0.001 (ΡΕ / Ρ0 (0.020, more preferably 0.001 ^ ΡΕ / Ρ0 (0.010, most preferably 0.001 ^ ΡΕ / Ρ0 (0.005.

[0132] 在本发明的烯烃聚合物的制造方法中,通过以表现聚合活性和α -烯烃聚合物的分子量提高效果的程度使微量的乙烯聚合,就可以制造高熔点的间规立构α-烯烃聚合物。 [0132] In the method for producing an olefin polymer according to the present invention, by the performance of the polymerization activity and α - effect of improving the degree of the molecular weight of olefin polymer a trace amount of the polymerization of ethylene, a high melting point can be produced syndiotactic α- olefin polymers. 如上所述,已知在茂金属催化剂聚合丙烯时,存在丙烯以2,1-插入的状态而反应停止的催化剂种,可以认为在聚合碳原子数为3~10的α -烯烃时,也存在成为类似的停止状态的催化剂种。 As described above, when a metallocene catalyst is known in the polymerization of propylene, catalyst species propylene and 2,1-insertion reaction was stopped state, it is considered that the polymerization of carbon atoms of α 3 ~ 10 - olefin, there become a similar kind of catalyst stop state. 其中,可以认为如果使上面规定量的乙烯反应,不仅能够将停止状态的催化剂种再活化而使活性提高,而且能够抑制聚合物链从催化剂种的脱离,因此可以使暂时停止的聚合物链的生长反应再次开始,其结果,α-烯烃聚合物的分子量增加。 Wherein, if the predetermined amount may be considered in the above reaction of ethylene, the catalyst not only stopped the states reactivation activity increased, but also possible to prevent the catalyst from the polymer chain thereof, the polymer chains can be temporarily stopped in the reaction began to grow again, as a result, the molecular weight of α- olefin polymer is increased. 另外,出乎意料的是相比于制造全同立构α-烯烃聚合物,其特征在于,在制造间规立构α-烯烃聚合物时,可以看到显著提高的效果。 Further, unexpectedly, as compared to α- producing isotactic olefin polymer, wherein, when inter-producing syndiotactic α- olefin polymer can be seen that significantly improved results.

[0133] <烯烃聚合物> [0133] <Olefin Polymer>

[0134] 接着,说明由本发明的制造方法得到的烯烃聚合物。 [0134] Next, the olefin polymer obtained by the production method of the present invention. 由本发明的制造方法制造的烯烃聚合物具有下述4个特征。 An olefin polymer produced by the production method of the present invention has the following four characteristics.

[0135][特征 I] [0135] [wherein I]

[0136] 其是包含源自选自碳原子数为3~10的α-烯烃中的至少I种以上的α _烯烃的结构单元X和源自乙烯的结构单元Y的聚合物,其特征在于,将在聚合物中占有的结构单元X的含量设为X (mol%),将在聚合物中占有的结构单元Y的含量设为y (mol%)时,98.5≤X≤99.9且1.5≤y≤0.1,且x+y= 100,优选为98.6≤x≤99.9且1.4≤y≤0.1,且x+y = 100,更优选为98.7≤X≤99.9且1.3≤y≤0.1,且x+y = 100,最优选为98.8≤X≤99.9且1.2≤y≤0.1,且x+y = 100。 [0136] which are selected from carbon atoms and comprising at least a polymer thereof or more [alpha] _ I-olefin structural unit X and Y of a structural unit derived from ethylene α- olefin having 3 to 10, characterized in that when the content in the polymer occupied by the structural unit X is defined as X (mol%), the content of the structural unit Y in the polymer to occupy y (mol%), 98.5≤X≤99.9 and 1.5≤ y≤0.1, and x + y = 100, and preferably 98.6≤x≤99.9 1.4≤y≤0.1, and x + y = 100, and more preferably 98.7≤X≤99.9 1.3≤y≤0.1, and x + y = 100, and most preferably 98.8≤X≤99.9 and 1.2≤y≤0.1, and x + y = 100. 由本发明的制造方法制造的烯烃聚合物,尽管包含微量源自乙烯的单元,还维持着高外消旋二单元组分率、高熔点,分子量也提高。 An olefin polymer produced by the production method of the present invention, although trace comprises units derived from ethylene, also maintains a high racemic diad fraction, high melting point, the molecular weight increase. 烯烃聚合物中的乙烯含量y大于规定范围时,因为不仅烯烃聚合物的熔点下降,而且结晶温度(Tc)也下降,所以成型加工性可能会恶化。 The ethylene content of the olefin polymer y is greater than a predetermined range, not only because the melting point of the olefin polymer is lowered, and the crystallization temperature (Tc) is also decreased, so that moldability may be deteriorated.

[0137][特征 2] [0137] [wherein 2]

[0138] 以由13C-NMR测定的外消旋二单元组分率([r])为90%≤[r]< 100%为特征,优选为95%≤[r] < 100%,更优选为97%≤[r] < 100%,最优选为98%≤[r] < 100%。 [0138] In the racemic diad fraction measured by 13C-NMR ([r]) was 90% ≤ [r] <100% is characterized, preferably 95% ≤ [r] <100%, more preferably为97%≤[r] < 100%,最优选为98%≤[r] < 100%。 由本发明的制造方法制造的烯烃聚合物,因为外消旋二单元组分率高,所以尽管包含微量源自乙烯的单元,还维持着高熔点。 An olefin polymer produced by the production method of the present invention, since the two-component high rac unit, although it contains trace amount of units derived from ethylene, also maintained a high melting point.

[0139][特征 3]

[0140]以由135°C的十氢化萘溶液测得的特性粘度([η ])为0.70dl/g以上为特征。 [0140] In ([[eta]]) of decalin solution viscosity measured to 135 ° C of 0.70dl / g or more is characterized.优选为0.75dl/g以上,更优选为0.80dl/g以上,最优选为0.85dl/g以上。分子量高的烯烃聚合物可以期待显示良好的强度和成型加工性。

[0141][特征 4]

[0142] 以由差示扫描量热计(DSC)求出的熔点(Tm)为145 °C以上为特征,优选为Tm≥147°C,更优选为Tm≥149°C,最优选为Tm≥151°C。 [0142] In a differential scanning calorimeter (DSC) determined point (Tm) of not less than 145 ° C wherein, preferably Tm≥147 ° C, more preferably Tm≥149 ° C, and most preferably Tm ≥151°C。 由本发明的制造方法制造的烯烃聚合物,尽管包含微量源自乙烯的单元,还维持着高外消旋二单元组分率、高熔点,分子 An olefin polymer produced by the production method of the present invention, although trace comprising units derived from ethylene, also maintains a high racemic diad fraction, melting point, molecular

量也提高。 Volume also increased.

[0143] 本发明的烯烃聚合物,尽管包含微量源自乙烯的单元,还维持着高外消旋二单元组分率、高熔点,分子量也高,可以认为这是因为α-烯烃的排列是间规立构的缘故。 [0143] an olefin polymer according to the present invention, although trace comprising units derived from ethylene, also maintains a high racemic diad fraction, melting point, molecular weight is high, it is believed this is because the arrangement is α- olefin syndiotactic sake. 作为间规立构结构的特征,已知如上所述能够采取螺旋结构、平面锯齿形结构等多个能量上稳定的晶体结构,还可以在一部分晶体结构之间可逆地相转移。 As a feature of the syndiotactic structure, is known as described above can be taken to stabilize the crystal structure of the plurality of energy helical structure, planar zigzag structures, etc., may also be reversibly phase transfer between a portion of the crystal structure. 全同立构聚丙烯时,因为以3分子丙烯旋转I周的螺旋结构处于优势位置,所以在其中含有微量源自乙烯的单元时,会对构成的晶体结构产生大的影响,熔点容易下降,相对于此,在间规立构聚丙烯时,推测通过能够采取多个能量上稳定的晶体结构而将源自乙烯的单元给予晶体结构的影响最小化,作为其结果,熔点变得难以下降。 When isotactic polypropylene, propylene since the spiral structure rotating 3 weeks I molecule in a dominant position, so when it contains trace amounts isotactic units derived from ethylene, a large configuration will affect the crystal structure, the melting point tends to decrease, in contrast, when the syndiotactic polypropylene, can be estimated by taking a stable crystal structure over the plurality of energy units derived from ethylene administering to minimize the influence of the crystal structure, as a result, it becomes difficult to decrease the melting point. 另外,因为同样的效果在丙烯以外的间规立构α-烯烃聚合物也可见,所以可以认为这在间规立构结构中为特征现象。 Further, because the same effect syndiotactic α- olefin than propylene in the polymer can also be found, it is considered that this phenomenon is characterized by the syndiotactic configuration.

[0144] 实施例 [0144] Example

[0145] 以下,基于实施例,更具体地说明本发明,但本发明不受这些实施例限定。 [0145] Hereinafter, the embodiments of the present invention more specifically, but the present invention is not limited to these examples. 首先,说明测定由本发明的制造方法得到的烯烃聚合物的物性的方法。 First, measuring methods of physical properties of olefin polymers obtained by the production method of the present invention.

[0146] <特性粘度[11]> [0146] <Intrinsic viscosity [11]>

[0147] 其为使用十氢化萘溶剂在135°C测得的值。 [0147] the value of a decalin solvent at 135 ° C measured.

[0148] <熔点(Tm)、结晶温度(Tc)、熔化热(ΛΗ (Tm)) > [0148] <melting point (Tm), crystallization temperature (Tc), heat of fusion (ΛΗ (Tm))>

[0149] 对于4-甲基-1-戊烯聚合物,使用精工电子纳米科技株式会社(SIINanoTechnology Inc.)生产的差示扫描量热计EXSTAR6000DSC,在氮气气流下(20mL/min),以IO0C /分钟将试样(约5mg)升温到270°C,在270°C保持5分钟后,以-10°C /分钟冷却到0°C,在0°C保持5分钟后,以10°C /分钟升温到270°C。 [0149] For 4-methyl-1-pentene polymer, produced by SII Nanotechnology Inc. (SIINanoTechnology Inc.) differential scanning calorimeter EXSTAR6000DSC produced, under a stream of nitrogen (20mL / min), to IO0C / min a sample (approximately 5mg) was heated to 270 ° C, held at 270 ° C 5 min to -10 ° C / min was cooled to 0 ° C, 5 min at 0 ° C, to 10 ° C / min was heated to 270 ° C. 将此时的冷却时的结晶温度峰的顶点作为结晶温度(Tc)。 The apex of the crystallization temperature peak as the time of the cooling-crystallization temperature (Tc). 另外,将第2次升温时的结晶熔融峰的顶点作为熔点(Tm),从峰的积算值算出熔化热(ΛΗ (Tm))。 Further, the crystal melting peak apex during the second heating as a melting point (Tm), the peak of heat of fusion calculated from the integrated value (ΛΗ (Tm)).

[0150] 对于丙烯聚合物,使用精工电子纳米科技株式会社生产的差示扫描量热计EXSTAR6000DSC,在氮气气流下(20mL/min),以10°C /分钟将试样(约5mg)升温到230°C,在230°C保持10分钟后,以-10°C /分钟冷却到30°C,在30°C保持5分钟后,以10°C /分钟升温到230°C。 [0150] For the propylene polymer, produced by SII Nanotechnology Co., Ltd. was a differential scanning calorimeter EXSTAR6000DSC, under a stream of nitrogen (20mL / min), at 10 ° C / min A sample (approximately 5mg) was heated to 230 ° C, held at 230 ° C for 10 minutes, at -10 ° C / min was cooled to 30 ° C, 5 min at 30 ° C, at 10 ° C / min temperature increase to 230 ° C. 将此时的冷却时的结晶温度峰的顶点作为结晶温度(Tc)。 The apex of the crystallization temperature peak as the time of the cooling-crystallization temperature (Tc). 另外,将第2次升温时的结晶熔融峰的顶点作为熔点(Tm),从峰的积算值算出熔化热(ΛΗ (Tm))。 Further, the crystal melting peak apex during the second heating as a melting point (Tm), the peak of heat of fusion calculated from the integrated value (ΛΗ (Tm)).

[0151] 另外,在实施例和比较例所得到的烯烃聚合物中,观察到2个以上的结晶熔融峰时,将最高熔点侧的峰的顶点定义为烯烃聚合物的熔点(Tm)。 When [0151] Further, the olefin polymer in Examples and Comparative Examples thus obtained was observed in two or more crystal melting peak, the peak apex of the highest melting point side defined as the melting point of the olefin polymer (Tm).

[0152] <立构规整性和乙烯含量> [0152] <stereoregularity and an ethylene content of>

[0153]以邻二氯苯-d4/苯_d6 (4/1 [v/v])和1,1,2,2_四氯乙烧_d2为测定溶剂,通过在测定温度120°C测定13C-NMR光谱(125MHz、日本电子生产ECP500型和100MHz、日本电子生产ECX400P型)算出烯烃聚合物的外消旋二单元组分率([r])。 [0153] o-dichlorobenzene -d4 / benzene _d6 (4/1 [v / v]) and B 1,1,2,2_ tetrachloro burning _d2 solvent is measured by measuring the temperature at 120 ° C Determination of 13C-NMR spectrum (125MHz, JEOL type and production ECP500 100MHz, JEOL ECX400P production type) is calculated racemic diad fraction olefin polymer ([r]). 其中,忽略乙烯插入的影响来计算。 Wherein insertion ignored Ethylene calculated. 例如,关于以4-甲基-1-戊烯为主要成分的聚合物,如果将来自外消旋结构的信号(42.7ppm附近)的积分值设为A,将来自内消旋结构的信号(42.4ppm附近)的积分值设为B,则作为内消旋二单元组分率([m]) /外消旋二单元组分率([r]) = B/Α且[m] + [r]= 100算出。 For example, with respect to 4-methyl-1-pentene polymer as a main component, if the integrated value from the signal (near 42.7ppm) racemic structure is A, the signal from the meso structure ( near 42.4ppm) integral value is set to B, the a meso diad fraction ([m]) / racemic diad fraction ([r]) = B / Α and [m] + [ r] = 100 was calculated. 关于以丙烯为主要成分的聚合物,可以参考公知的文献算出。 About propylene polymer as a main component, it can be calculated from known literature reference. 另外乙烯含量由13C-NMR 光谱,参考(Macromolecules, 1982,15,1150)求出。 Further ethylene content was determined from 13C-NMR spectrum, the reference (Macromolecules, 1982,15,1150). [0154] <摩尔分数> [0154] <mole fraction>

[0155] 在碳原子数为3~10的α -烯烃中,例示作为气体的例子使用丙烯的情况,例示作为液体的例子使用4-甲基-1-戊烯的情况。 [0155] In the carbon atoms of α 3 ~ 10 - olefin in the example illustrated using propene as a gas, the situation illustrated using 4-methylpentene-1 as an example of liquid. 如上所述,丙烯的情况下,将供给的乙烯的摩尔数设为Me,将供给的丙烯的摩尔数设为Mtj,作为摩尔分数仏/X =(乙烯流量/丙烯流量)算出。 As described above in the case of propylene, the number of moles of ethylene fed to Me, the number of moles of propylene supplied to Mtj, as the mole fraction Fo / X = (flow rate of ethylene / propylene flow) was calculated. 另外,4-甲基-1-戊烯的情况下,将供给的乙烯的摩尔数设为Pe,将4-甲基-1-戊烯的摩尔数设为匕,作为摩尔分数PeA^ =(乙烯流量/ 4-甲基-1-戊烯的加入量)算出。 Further, 4-methyl-1-pentene in the case of the number of moles of ethylene fed to Pe, the number of moles of 4-methyl-1-pentene set dagger, a mole fraction PeA ^ = ( the flow amount of ethylene / 4-methyl-1-pentene) was calculated.

[0156] <过渡金属化合物(A) > [0156] <transition metal compound (A)>

[0157] 过渡金属化合物(A)以在以下的日本专利公报中记载的方法合成。 [0157] The transition metal compound (A) synthesized in the method described in Japanese Patent Publication. 日本特开2000-212194号公报、日本特开2004-168744号公报、日本特开2004-189666号公报、日本特开2004-161957号公报、日本特开2007-302854号公报、日本特开2007-302853号公报、W001/027124号公报、日本特表2001-526730号公报、日本特开平10-226694号公报。 Japanese Unexamined Patent Publication No. 2000-212194, Japanese Patent Laid-open No. 2004-168744, Japanese Patent Laid-open No. 2004-189666, Japanese Patent Laid-open No. 2004-161957, Japanese Patent Laid-open No. 2007-302854, Japanese Unexamined 2007- Publication No. 302853, W001 / Publication No. 027,124, Japanese Unexamined Patent Publication No. 2001-526730, Japanese Laid-Open Patent Publication No. 10-226694.

[0158] 过渡金属化合物(al):二苄基亚甲基(环戊二烯基)(3,6-二叔丁基芴基)二氯化锆 [0158] The transition metal compound (al): dibenzylmethylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride

Figure CN102686615BD00201

[0160] 过渡金属化合物(a2): 二苄基亚甲基(环戊二烯基)(2,7-二对氯苯基-3,6-二叔 [0160] The transition metal compound (a2): dibenzylmethylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6

丁基芴基)二氯化锆 Butyl fluorenyl) zirconium dichloride

[0161] [0161]

Figure CN102686615BD00202

[0162] 过渡金属化合物(a3):二苯基亚甲基(3-叔丁基-5-甲基环戊二烯基)(2,7_ 二叔丁基芴基)二氯化锆 [0162] The transition metal compound (a3): diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7_ di-tert-fluorenyl) zirconium dichloride

[0163] [0163]

Figure CN102686615BD00211

[0164] 过渡金属化合物(a4):二苄基亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基 [0164] The transition metal compound (a4): dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butyl

芴基)二氯化锆 Fluorenyl) zirconium dichloride

[0165] [0165]

Figure CN102686615BD00212

[0166] 过渡金属化合物(a5): 二对氯苄基亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔 [0166] The transition metal compound (a5): two p-chlorobenzyl methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t

丁基芴基)二氯化锆 Butyl fluorenyl) zirconium dichloride

[0167] [0167]

Figure CN102686615BD00213

[0168][实施例1] [0168] [Example 1]

[0169] [4-甲基-1-戊烯聚合物的制造] [0169] [4-methyl-1-pentene polymer for producing a]

[0170] 在氮充分置换过的内容量500mL的玻璃制高压釜(附有玻璃制吹入管)中加入4-甲基-1-戊烯200mL,保持在30°C。 [0170] In a sufficiently nitrogen-purged glass autoclave of 500mL (equipped with a glass gas inlet tube) was added 4-methyl-1-pentene 200mL, maintained at 30 ° C. 另一方面,在氮充分置换过的内容量30mL的支管烧瓶中加入磁力搅拌子,在其中加入1.31mL (Al = 2mmol) Tosoh-finechem生产的甲基招氧烷的己烷溶液(Al浓度:1.52mol/L),接着,加入2.79mg (0.004mmol)二苄基亚甲基(环戊二烯基)(3,6- 二叔丁基芴基)二氯化锆和2mL脱水甲苯,搅拌10分钟。 On the other hand, a magnetic stirrer was added at a sufficiently nitrogen-purged 30mL flask branch pipe, in which the addition of 1.31mL (Al = 2mmol) in hexane Tosoh-finechem production of methyl alumoxane strokes (Al concentration: 1.52mol / L), then was added 2.79mg (0.004mmol) of dibenzylmethylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stirring 10 minutes. 在预先使氮流通的高压釜中添加1.0mmol三异丁基铝的甲苯溶液(Al = 1.0M),接着,在高压釜中加入上述溶液,从玻璃制吹入管使氮2.5NL/h、乙烯0.5NL/h的混合气体流通,开始聚合。 1.0mmol of triisobutylaluminum was added in a stream of nitrogen advance autoclave a toluene solution (Al = 1.0M), then added to this solution in the autoclave, nitrogen gas inlet tube 2.5NL / h, ethylene from glass 0.5NL / h of gas mixture flow, to initiate polymerization. 因为聚合气氛中的P。 Because the polymerization atmosphere P. = 1.5875,Pe = 0.0037,所以算出PE/PQ = 0.0023。 = 1.5875, Pe = 0.0037, so calculated PE / PQ = 0.0023. 氮和乙烯的混合气体在聚合中也连续地供给,在常压下、30°C进行10分钟聚合后,添加少量异丁醇停止聚合。 After a mixed gas of nitrogen and ethylene was continuously fed during polymerization at normal pressure, 30 ° C for 10 minutes of polymerization, a small amount of isobutanol was added to terminate the polymerization. 在包含ImL盐酸的1.5L甲醇中加入聚合物溶液,使4-甲基-1-戊烯聚合物析出。 1.5L methanol was added to the polymer solution containing ImL of hydrochloric acid, 4-methyl-1-pentene polymer precipitated. 将其在80°C进行10小时减压干燥,结果得到4-甲基-1-戍烯聚合物4.90g。 Which was dried under reduced pressure for 10 hours at 80 ° C, the resulting 4-methyl-pentene polymer 4.90g. 聚合活性为7.35kg/mmol-Zr *hr,得到的4-甲基-1-戊烯聚合物的[n] = 0.88dl/g、Tc = 153°C、Tm= 201°C> ΔΗ (Tm)=14.2mJ/mg、乙烯含量=0.2% > [r] = 98.2% „ The polymerization activity was 7.35kg / mmol-Zr * hr, 4- methylpentene-1 polymer obtained [n] = 0.88dl / g, Tc = 153 ° C, Tm = 201 ° C> ΔΗ (Tm ) = 14.2mJ / mg, ethylene content = 0.2%> [r] = 98.2% "

[0171][实施例2] [0171] [Example 2]

[0172] [4-甲基-1-戊烯聚合物的制造] [0172] [4-methyl-1-pentene polymer for producing a]

[0173] 在氮充分置换过的内容量500mL的玻璃制高压釜(附有玻璃制吹入管)中加入4-甲基-1-戊烯200mL,保持在30°C。 [0173] In a sufficiently nitrogen-purged glass autoclave of 500mL (equipped with a glass gas inlet tube) was added 4-methyl-1-pentene 200mL, maintained at 30 ° C. 另一方面,在氮充分置换过的内容量30mL的支管烧瓶中加入磁力搅拌子,在其中加入1.31mL (Al = 2mmol) Tosoh-finechem生产的甲基招氧烷的己烷溶液(Al浓度:1.52mol/L),接着,加入2.79mg (0.004mmol) 二苄基亚甲基(环戊二烯基)(3,6- 二叔丁基芴基)二氯化锆和2mL脱水甲苯,搅拌10分钟。 On the other hand, a magnetic stirrer was added at a sufficiently nitrogen-purged 30mL flask branch pipe, in which the addition of 1.31mL (Al = 2mmol) in hexane Tosoh-finechem production of methyl alumoxane strokes (Al concentration: 1.52mol / L), then was added 2.79mg (0.004mmol) of dibenzylmethylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stirring 10 minutes. 在预先使氮流通的高压釜中添加1.0mmol三异丁基铝的甲苯溶液(Al = 1.0M),接着,在高压釜中加入上述溶液,从玻璃制吹入管使氮10NL/h、乙烯2NL/h的混合气体流通,开始聚合。 1.0mmol of triisobutylaluminum was added in a stream of nitrogen advance autoclave a toluene solution (Al = 1.0M), then added to this solution in the autoclave, nitrogen gas inlet tube 10NL / h, from the glass ethylene 2NL / h of gas mixture flow, to initiate polymerization. 聚合气氛中的P。 In the polymerization atmosphere P. = 1.5875,Pe = 0.0074,算出PE/PQ = 0.0047。 = 1.5875, Pe = 0.0074, the calculated PE / PQ = 0.0047. 氮和乙烯的混合气体在聚合中也连续地供给,在常压下、30°C进行5分钟聚合后,添加少量异丁醇停止聚合。 After a mixed gas of nitrogen and ethylene was continuously fed during polymerization at normal pressure, 30 ° C for 5 minutes polymerization, a small amount of isobutanol was added to terminate the polymerization. 在包含ImL盐酸的 Hydrochloric acid containing ImL

1.5L甲醇中加入聚合物溶液,使4-甲基-1-戊烯聚合物析出。 1.5L methanol was added to the polymer solution, 4-methyl-1-pentene polymer precipitated. 将其在80°C进行10小时减压干燥,结果得到4-甲基-1-戍烯聚合物2.59g。 Which was dried under reduced pressure for 10 hours at 80 ° C, the resulting 4-methyl-pentene polymer 2.59g. 聚合活性为7.77kg/mmol-Zr.1ί;r,得到的4-甲基-1-戊烯聚合物的特性粘度[n] = 0.98dl/g、Tc = 149°C、Tm = 199°C、ΛΗ (Tm)=15.lmj/mg、乙烯含量=0.4% > [r] = 97.7% „ The polymerization activity was 7.77kg / mmol-Zr.1ί; r, to give the 4-methyl-intrinsic viscosity [n] pentene polymer = 0.98dl / g, Tc = 149 ° C, Tm = 199 ° C , ΛΗ (Tm) = 15.lmj / mg, ethylene content = 0.4%> [r] = 97.7% "

[0174][实施例3] [0174] [Example 3]

[0175] [4-甲基-1-戊烯聚合物的制造] [0175] [4-methyl-1-pentene polymer for producing a]

[0176] 在氮充分置换过的内容量500mL的玻璃制高压釜(附有玻璃制吹入管)中加入4-甲基-1-戊烯200mL,保持在30°C。 [0176] In a sufficiently nitrogen-purged glass autoclave of 500mL (equipped with a glass gas inlet tube) was added 4-methyl-1-pentene 200mL, maintained at 30 ° C. 另一方面,在氮充分置换过的内容量30mL的支管烧瓶中加入磁力搅拌子,在其中加入1.31mL (Al = 2mmol) Tosoh-finechem生产的甲基招氧烷的己烷溶液(Al浓度:1.52mol/L),接着,加入2.79mg (0.004mmol) 二苄基亚甲基(环戊二烯基)(3,6- 二叔丁基芴基)二氯化锆和2mL脱水甲苯,搅拌10分钟。 On the other hand, a magnetic stirrer was added at a sufficiently nitrogen-purged 30mL flask branch pipe, in which the addition of 1.31mL (Al = 2mmol) in hexane Tosoh-finechem production of methyl alumoxane strokes (Al concentration: 1.52mol / L), then was added 2.79mg (0.004mmol) of dibenzylmethylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stirring 10 minutes. 在预先使氮流通的高压釜中添加1.0mmol三异丁基铝的甲苯溶液(Al = 1.0M),接着,在高压釜中加入上述溶液,从玻璃制吹入管使氮10NL/h、乙烯6NL/h的混合气体流通,开始聚合。 1.0mmol of triisobutylaluminum was added in a stream of nitrogen advance autoclave a toluene solution (Al = 1.0M), then added to this solution in the autoclave, nitrogen gas inlet tube 10NL / h, ethylene 6NL from glass / h of gas mixture flow, to initiate polymerization. 聚合气氛中的P。 In the polymerization atmosphere P. = 1.5875,Pe = 0.0223,算出PE/PQ = 0.0141。 = 1.5875, Pe = 0.0223, the calculated PE / PQ = 0.0141. 氮和乙烯的混合气体在聚合中也连续地供给,在常压下、30°C进行5分钟聚合后,添加少量异丁醇停止聚合。 After a mixed gas of nitrogen and ethylene was continuously fed during polymerization at normal pressure, 30 ° C for 5 minutes polymerization, a small amount of isobutanol was added to terminate the polymerization. 在包含ImL盐酸的 Hydrochloric acid containing ImL

1.5L甲醇中加入聚合物溶液,使4-甲基-1-戊烯聚合物析出。 1.5L methanol was added to the polymer solution, 4-methyl-1-pentene polymer precipitated. 将其在80°C进行10小时减压干燥,结果得到4-甲基-1-戍烯聚合物2.96g。 Which was dried under reduced pressure for 10 hours at 80 ° C, the resulting 4-methyl-pentene polymer 2.96g. 聚合活性为8.88kg/mmol-Zr.1ί;fr,得到的4-甲基-1-戊烯聚合物的特性粘度[Π] = 1.10dl/g、Tc = 143°C、Tm= 197°C、ΔΗ (Tm)=13.7mJ/mg、乙烯含量=0.6% > [r] = 97.6% „ The polymerization activity was 8.88kg / mmol-Zr.1ί; fr, to give 4-methyl-1-pentene polymer having an intrinsic viscosity [Π] = 1.10dl / g, Tc = 143 ° C, Tm = 197 ° C , ΔΗ (Tm) = 13.7mJ / mg, ethylene content = 0.6%> [r] = 97.6% "

[0177][实施例4] [0177] [Example 4]

[0178] [4-甲基-1-戊烯聚合物的制造] [0178] [4-methyl-1-pentene polymer for producing a]

[0179]在氮充分置换过的内容量500mL的玻璃制高压釜(附有玻璃制吹入管)中加入4-甲基-1-戊烯200mL,保持在30°C。 [0179] In a sufficiently nitrogen-purged glass autoclave of 500mL (equipped with a glass gas inlet tube) was added 4-methyl-1-pentene 200mL, maintained at 30 ° C. 另一方面,在氮充分置换过的内容量30mL的支管烧瓶中加入磁力搅拌子,在其中加入1.31mL (Al = 2mmol) Tosoh-finechem生产的甲基招氧烷的己烷溶液(Al浓度:1.52mol/L),接着,加入2.79mg (0.004mmol)二苄基亚甲基(环戊二烯基)(3,6- 二叔丁基芴基)二氯化锆和2mL脱水甲苯,搅拌10分钟。 On the other hand, a magnetic stirrer was added at a sufficiently nitrogen-purged 30mL flask branch pipe, in which the addition of 1.31mL (Al = 2mmol) in hexane Tosoh-finechem production of methyl alumoxane strokes (Al concentration: 1.52mol / L), then was added 2.79mg (0.004mmol) of dibenzylmethylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stirring 10 minutes. 在预先使氮流通的高压釜中添加1.0mmol三异丁基铝的甲苯溶液(Al = 1.0M),接着,在高压釜中加入上述溶液,从玻璃制吹入管使氮10NL/h、乙烯10NL/h的混合气体流通,开始聚合。 1.0mmol of triisobutylaluminum was added in a stream of nitrogen advance autoclave a toluene solution (Al = 1.0M), then added to this solution in the autoclave, nitrogen gas inlet tube 10NL / h, ethylene 10NL from glass / h of gas mixture flow, to initiate polymerization. 作为聚合气氛中的P。 As the polymerization atmosphere P. = 1.5875、Pe =乙烯的摩尔数=0.0372,算出PE/PQ = 0.0234。 = 1.5875, Pe = = 0.0372 moles of ethylene, is calculated PE / PQ = 0.0234. 氮和乙烯的混合气体在聚合中也连续地供给,在常压下、30°C进行5分钟聚合后,添加少量异丁醇停止聚合。 After a mixed gas of nitrogen and ethylene was continuously fed during polymerization at normal pressure, 30 ° C for 5 minutes polymerization, a small amount of isobutanol was added to terminate the polymerization. 在包含ImL盐酸的1.5L甲醇中加入聚合物溶液,使4-甲基-1-戊烯聚合物析出。 1.5L methanol was added to the polymer solution containing ImL of hydrochloric acid, 4-methyl-1-pentene polymer precipitated. 将其在80°C进行10小时减压干燥,结果得到4-甲基-1-戊烯聚合物3.18g。 Which was dried under reduced pressure for 10 hours at 80 ° C, the resulting 4-methyl-1-pentene polymer 3.18g. 聚合活性为9.54kg/mmol-Zr.hr,得到的4_甲基-1-戍烯聚合物的特性粘度[η ] = 1.18dl/g、Tc = 139。 The polymerization activity was 9.54kg / mmol-Zr.hr, 4_ intrinsic viscosity of methyl-1-pentene polymer obtained [η] = 1.18dl / g, Tc = 139. . 、Tm = 195°C、Δ H (Tm) = 12.7mJ/mg、乙烯含量=1.0% > [r] = 97.9% „ , Tm = 195 ° C, Δ H (Tm) = 12.7mJ / mg, ethylene content = 1.0%> [r] = 97.9% "

[0180][比较例1] [0180] [Comparative Example 1]

[0181] [4-甲基-1-戊烯聚合物的制造] [0181] [4-methyl-1-pentene polymer for producing a]

[0182] 在氮充分置换过的内容量500mL的玻璃制高压釜(附有玻璃制吹入管)中加入4-甲基-1-戊烯200mL,保持在30°C。 [0182] In a sufficiently nitrogen-purged glass autoclave of 500mL (equipped with a glass gas inlet tube) was added 4-methyl-1-pentene 200mL, maintained at 30 ° C. 另一方面,在氮充分置换过的内容量30mL的支管烧瓶中加入磁力搅拌子,在其中加入1.31mL (Al = 2mmol) Tosoh-finechem生产的甲基招氧烷的己烷溶液(Al浓度:1.52mol/L),接着,加入2.79mg (0.004mmol)二苄基亚甲基(环戊二烯基)(3,6- 二叔丁基芴基)二氯化锆和2mL脱水甲苯,搅拌10分钟。 On the other hand, a magnetic stirrer was added at a sufficiently nitrogen-purged 30mL flask branch pipe, in which the addition of 1.31mL (Al = 2mmol) in hexane Tosoh-finechem production of methyl alumoxane strokes (Al concentration: 1.52mol / L), then was added 2.79mg (0.004mmol) of dibenzylmethylene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconium dichloride and 2mL dehydrated toluene, stirring 10 minutes. 在预先使氮流通的高压釜中添加1.0mmol三异丁基铝的甲苯溶液(Al = 1.0M),接着,在高压釜中加入上述溶液,从玻璃制吹入管使氮50NL/h流通,开始聚合。 1.0mmol of triisobutylaluminum was added in a stream of nitrogen advance autoclave a toluene solution (Al = 1.0M), then added to this solution in an autoclave, the glass blowing tube nitrogen 50NL / h flow begins polymerization. 氮在聚合中也连续地供给,在常压下、30°C进行30分钟聚合后,添加少量异丁醇停止聚合。 After nitrogen was continuously fed during polymerization at normal pressure, 30 ° C for 30 minutes the polymerization, a small amount of isobutanol was added to terminate the polymerization. 在包含1mL盐酸的1.5L甲醇中加入聚合物溶液,使4-甲基-1-戊烯聚合物析出。 1.5L methanol was added to the polymer solution containing hydrochloric acid 1mL, 4-methyl-1-pentene polymer precipitated. 将其在80°C进行10小时减压干燥,结果得到4-甲基-1-戍烯聚合物0.43g。 Which was dried under reduced pressure for 10 hours at 80 ° C, the resulting 4-methyl-pentene polymer 0.43g. 聚合活性为0.22kg/mmol-Zr ^hr,得到的4-甲基_1_戍烯聚合物的特性粘度[η] = 0.60dl/g、Tc = 155°C、Tm = 204。 The polymerization activity was 0.22kg / mmol-Zr ^ hr, the intrinsic viscosity _1_ 4-methyl-pentene obtained polymer [η] = 0.60dl / g, Tc = 155 ° C, Tm = 204. . 、ΔΗ (Tm) = 20.3mJ/mg、乙烯含量=0.0% > [r] = 98.0%。 , ΔΗ (Tm) = 20.3mJ / mg, ethylene content = 0.0%> [r] = 98.0%.

[0183][比较例2] [0183] [Comparative Example 2]

[0184] [4-甲基-1-戊烯聚合物的制造] [0184] [4-methyl-1-pentene polymer for producing a]

[0185] 从玻璃制吹入管使氮10NL/h、乙烯100NL/h的混合气体流通,聚合气氛中的PE/PQ=0.2340,除此以外,按照实施例1进行实验。 [0185] blown from a tube made of glass so that nitrogen 10NL / h, the mixed gas of ethylene 100NL / h flow, a polymerization atmosphere PE / PQ = 0.2340, except experiment as in Example 1.

[0186][比较例3] [0186] [Comparative Example 3]

[0187] [4-甲基-1-戊烯聚合物的制造] [0187] [4-methyl-1-pentene polymer for producing a]

[0188] 从玻璃制吹入管使乙烯150NL/h的混合气体流通,聚合气氛中的PE/PQ = 0.2808,除此以外,按照实施例1进行实验。 [0188] From a glass blowing tube, a mixed gas of ethylene 150NL / h flow, a polymerization atmosphere PE / PQ = 0.2808, except experiment as in Example 1.

[0189][实施例5] [0189] [Example 5]

[0190][丙烯聚合物的制造] [0190] [Production of Propylene Polymer]

[0191] 在氮充分置换过的内容量500mL的玻璃制高压釜(附有玻璃制吹入管)中加入400mL庚烷,保持在50°C。 [0191] 400mL of heptane was added in a sufficiently nitrogen-purged glass autoclave of 500mL (equipped with a glass gas inlet tube), maintained at 50 ° C. 另一方面,在氮充分置换过的内容量30mL的支管烧瓶中加入磁力搅拌子,在其中加入2.62mL (Al = 4mmol) Tosoh-finechem生产的甲基招氧烧的己烧溶液(Al浓度:1.52mol/L),接着,加入3.67mg (0.004mmol) 二苄基亚甲基(环戊二烯基)(2,7- 二对氯苯基-3,6- 二叔丁基芴基)二氯化锆和2mL脱水甲苯,搅拌10分钟。 On the other hand, a magnetic stirrer was added at a sufficiently nitrogen-purged 30mL flask branch pipe, in which the addition of 2.62mL (Al = 4mmol) Tosoh-finechem strokes of methylaluminoxane had an oxygen burn burn solution (Al concentration: 1.52mol / L), followed by addition of 3.67 mg (0.004 mmol) of dibenzylmethylene (cyclopentadienyl) (2,7-p-chlorophenyl-3,6-di-tert-fluorenyl) zirconium dichloride and 2mL of dehydrated toluene, stirred for 10 minutes. 在预先使氮流通的高压釜中添加1.0mrnol三异丁基铝的甲苯溶液(Al = 1.0M),接着,在高压釜中加入上述溶液,从玻璃制吹入管使丙烯150NL/h、乙烯INL/h的混合气体流通,开始聚合。 1.0mrnol added triisobutylaluminum in which nitrogen flow autoclave a toluene solution (Al = 1.0M), then added to this solution in the autoclave, propylene blowing tube 150NL / h, ethylene INL from glass / h of gas mixture flow, to initiate polymerization. 算出聚合气氛中的PeA^ = 0.0067。 Calculating the polymerization atmosphere PeA ^ = 0.0067. 丙烯/乙烯混合气体在聚合中也连续地供给,在常压下、50°C进行15分钟聚合后,添加少量异丁醇停止聚合。 After the propylene / ethylene mixture gas was continuously fed during polymerization at normal pressure, 50 ° C for 15 minutes of polymerization, a small amount of isobutanol was added to terminate the polymerization. 在包含ImL盐酸的1.5L甲醇中加入聚合物溶液,使丙烯聚合物析出。 1.5L methanol was added to the polymer solution containing ImL hydrochloric acid, the propylene polymer precipitated. 得到的丙烯聚合物在80°C进行10小时减压干燥,结果得到 The propylene polymer for 10 hours at 80 ° C under reduced pressure and dried to give

3.76g丙烯聚合物。 3.76g propylene polymer. 聚合活性为3.76kg/mmol-Zr -hr,得到的丙烯聚合物的[η ]= 1.57dl/g、Tc = 102°C、Tm = 155°C、Δ H (Tm) = 51.6mJ/mg、乙烯含量=0.5% > [r] = 98.0%。 The polymerization activity was 3.76kg / mmol-Zr -hr, obtained propylene polymer [η] = 1.57dl / g, Tc = 102 ° C, Tm = 155 ° C, Δ H (Tm) = 51.6mJ / mg, ethylene content = 0.5%> [r] = 98.0%.

[0192][实施例6] [0192] [Example 6]

[0193][丙烯聚合物的制造] [0193] [Production of Propylene Polymer]

[0194] 从玻璃制吹入管使丙烯150NL/h、乙烯0.8NL/h的混合气体流通,开始聚合,聚合气氛中的Pe/Po = 0.0053,除此以外,按照实施例5进行实验。 [0194] From a glass blowing tube propylene 150NL / h, the mixed gas of ethylene 0.8NL / h flow, to initiate polymerization, the polymerization atmosphere Pe / Po = 0.0053, except experiment was conducted as in Example 5.

[0195][实施例7] [0195] [Example 7]

[0196][丙烯聚合物的制造] [0196] [Production of Propylene Polymer]

[0197] 从玻璃制吹入管使丙烯150NL/h、乙烯1.5NL/h的混合气体流通,开始聚合,聚合气氛中的Pe/po = 0.0100,除此以外,按照实施例5进行实验。 [0197] From a glass blowing tube propylene 150NL / h, the mixed gas of ethylene 1.5NL / h flow, to initiate polymerization, the polymerization atmosphere Pe / po = 0.0100, except experiment was conducted as in Example 5.

[0198][实施例8] [0198] [Example 8]

[0199][丙烯聚合物的制造] [0199] [Production of Propylene Polymer]

[0200] 从玻璃制吹入管使丙烯150NL/h、乙烯4.0NL/h的混合气体流通,开始聚合,聚合气氛中的Pe/^ = 0.0267,除此以外,按照实施例5进行实验。 [0200] From a glass blowing tube propylene 150NL / h, the mixed gas of ethylene 4.0NL / h flow, to initiate polymerization, the polymerization atmosphere Pe / ^ = 0.0267, except experiment was conducted as in Example 5.

[0201][比较例4] [0201] [Comparative Example 4]

[0202][丙烯聚合物的制造] [0202] [Production of Propylene Polymer]

[0203] 从玻璃制吹入管仅使丙烯150NL/h流通,开始聚合,除此以外,按照实施例5进行实验。 [0203] From a glass blowing tube only propylene 150NL / h flow, to initiate polymerization, except that the experiment according to Example 5.

[0204][比较例5] [0204] [Comparative Example 5]

[0205][丙烯聚合物的制造] [0205] [Production of Propylene Polymer]

[0206] 从玻璃制吹入管使丙烯150NL/h、乙烯10.5NL/h的混合气体流通,开始聚合,聚合气氛中的Pe/^ = 0.0700,除此以外,按照实施例5进行实验。 [0206] From a glass blowing tube propylene 150NL / h, the mixed gas of ethylene 10.5NL / h flow, to initiate polymerization, the polymerization atmosphere Pe / ^ = 0.0700, except experiment was conducted as in Example 5.

[0207][实施例9] [0207] [Example 9]

[0208][丙烯聚合物的制造] [0208] [Production of Propylene Polymer]

[0209] 将过渡金属化合物设为(a4):二苄基亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆,从玻璃制吹入管使丙烯150NL/h、乙烯0.3NL/h的混合气体流通,开始聚合,聚合气氛中的Pe/^ = 0.0020,除此以外,按照实施例5进行实验。 [0209] The transition metal compound to (a4): dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride , glass blowing tube from propylene 150NL / h, the mixed gas of ethylene 0.3NL / h flow, to initiate polymerization, the polymerization atmosphere Pe / ^ = 0.0020, except experiment was conducted as in Example 5.

[0210][实施例 10] [0210] [Example 10]

[0211][丙烯聚合物的制造] [0211] [Production of Propylene Polymer]

[0212] 将过渡金属化合物设为(a4):二苄基亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆,除此以外,按照实施例5进行实验。 [0212] The transition metal compound to (a4): dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride except experiment according to Example 5.

[0213][比较例6] [0213] [Comparative Example 6]

[0214][丙烯聚合物的制造] [0214] [Production of Propylene Polymer]

[0215] 将过渡金属化合物设为(a4):二苄基亚甲基(环戊二烯基)(2,7-二苯基-3,6-二叔丁基芴基)二氯化锆,从玻璃制吹入管仅使丙烯150NL/h流通,开始聚合,除此以外,按照实施例5进行实验。 [0215] The transition metal compound to (a4): dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride , glass blowing tube from only propylene 150NL / h flow, to initiate polymerization, except that the experiment according to Example 5.

[0216][实施例 11] [0216] [Example 11]

[0217][丙烯聚合物的制造] [0217] [Production of Propylene Polymer]

[0218] 将过渡金属化合物设为(a5): 二对氯苄基亚甲基(环戊二烯基)(2,7-二苯基-3,6- 二叔丁基芴基)二氯化锆,从玻璃制吹入管使丙烯150NL/h、乙烯0.45NL/h的混合气体流通,开始聚合,聚合气氛中的PeA^ = 0.0033,除此以外,按照实施例5进行实验。 [0218] The transition metal compound to (a5): two p-chlorobenzyl methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butyl fluorenyl) dichloro zirconium, glass blowing tube from propylene 150NL / h, the mixed gas of ethylene 0.45NL / h flow, to initiate polymerization, the polymerization atmosphere PeA ^ = 0.0033, except experiment was conducted as in Example 5.

[0219][比较例7] [0219] [Comparative Example 7]

[0220][丙烯聚合物的制造] [0220] [Production of Propylene Polymer]

[0221] 将过渡金属化合物设为(a5): 二对氯苄基亚甲基(环戊二烯基)(2,7-二苯基-3,6- 二叔丁基芴基)二氯化锆,从玻璃制吹入管仅使150NL/h丙烯流通,开始聚合,除此以外,按照实施例5进行实验。 [0221] The transition metal compound to (a5): two p-chlorobenzyl methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butyl fluorenyl) dichloro zirconium, from only the glass blowing tube 150NL / h flow of propylene, initiate polymerization, except experiment according to Example 5.

[0222][参考例I] [0222] [Reference Example I]

[0223] [4-甲基-1-戊烯聚合物的制造] [0223] [4-methyl-1-pentene polymer for producing a]

[0224] 在氮充分置换过的内容量500mL的玻璃制高压釜(附有玻璃制吹入管)中加入4-甲基-1-戊烯200mL,保持在40°C。 [0224] In a sufficiently nitrogen-purged glass autoclave of 500mL (equipped with a glass gas inlet tube) was added 4-methyl-1-pentene 200mL, maintained at 40 ° C. 另一方面,在氮充分置换过的内容量30mL的支管烧瓶中加入磁力搅拌子,在其中加入1.31mL (Al = 2mmol) Tosoh-finechem生产的甲基招氧烷的己烷溶液(Al浓度:1.52mol/L),接着,加入2.96mg (0.004mmol)二苯基亚甲基(3-叔丁基-5-甲基环戊二烯基)(2,7- 二叔丁基芴基)二氯化锆和2mL脱水甲苯,搅拌10分钟。 On the other hand, a magnetic stirrer was added at a sufficiently nitrogen-purged 30mL flask branch pipe, in which the addition of 1.31mL (Al = 2mmol) in hexane Tosoh-finechem production of methyl alumoxane strokes (Al concentration: 1.52mol / L), followed by addition of 2.96 mg (0.004 mmol) of diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride and 2mL of dehydrated toluene, stirred for 10 minutes. 在预先使氮流通的高压爸中添加1.0mmol三异丁基招的甲苯溶液(Al = 1.0M),接着,在高压釜中加入上述溶液,从玻璃制吹入管使氮25NL/h流通,开始聚合。 Added 1.0mmol of triisobutyl move in advance of the high pressure nitrogen flow father in a toluene solution (Al = 1.0M), then added to this solution in an autoclave, the glass blowing nitrogen blowing tube 25NL / h flow begins polymerization. 氮在聚合中也连续地供给,在常压下、40°C进行30分钟聚合后,添加少量异丁醇停止聚合。 After nitrogen was continuously fed during polymerization under normal pressure, 40 ° C for 30 minutes of polymerization, a small amount of isobutanol was added to terminate the polymerization. 在包含ImL盐酸的 Hydrochloric acid containing ImL

1.5L甲醇中加入聚合物溶液,使4-甲基-1-戊烯聚合物析出。 1.5L methanol was added to the polymer solution, 4-methyl-1-pentene polymer precipitated. 将其在80°C进行10小时减压干燥,结果得到4-甲基-1-戍烯聚合物1.82g。 Which was dried under reduced pressure for 10 hours at 80 ° C, the resulting 4-methyl-pentene polymer 1.82g. 聚合活性为0.91kg/mmol-Zr.hr,得到的4-甲基-1-戊烯聚合物的特性粘度[n] = 2.04dl/g、Tc = 203°C、Tm = 232°C、ΔΗ (Tm)=27.8mJ/mg、乙烯含量=0.0% > [r] = 2.0% „ The polymerization activity was 0.91kg / mmol-Zr.hr, an intrinsic viscosity of 4-methyl-1-pentene polymer obtained [n] = 2.04dl / g, Tc = 203 ° C, Tm = 232 ° C, ΔΗ (Tm) = 27.8mJ / mg, ethylene content = 0.0%> [r] = 2.0% "

[0225][参考例2] [0225] [Reference Example 2]

[0226] 在氮充分置换过的内容量500mL的玻璃制高压釜(附有玻璃制吹入管)中加入4-甲基-1-戊烯200mL,保持在40°C。 [0226] In a sufficiently nitrogen-purged glass autoclave of 500mL (equipped with a glass gas inlet tube) was added 4-methyl-1-pentene 200mL, maintained at 40 ° C. 另一方面,在氮充分置换过的内容量30mL的支管烧瓶中加入磁力搅拌子,在其中加入1.31mL (Al = 2mmol) Tosoh-finechem生产的甲基招氧烷的己烷溶液(Al浓度:1.52mol/L),接着,加入2.96mg (0.004mmol)二苯基亚甲基(3-叔丁基-5-甲基环戊二烯基)(2,7- 二叔丁基芴基)二氯化锆和2mL脱水甲苯,搅拌10分钟。 On the other hand, a magnetic stirrer was added at a sufficiently nitrogen-purged 30mL flask branch pipe, in which the addition of 1.31mL (Al = 2mmol) in hexane Tosoh-finechem production of methyl alumoxane strokes (Al concentration: 1.52mol / L), followed by addition of 2.96 mg (0.004 mmol) of diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride and 2mL of dehydrated toluene, stirred for 10 minutes. 在预先使氮流通的高压爸中添加1.0mmol三异丁基招的甲苯溶液(Al = 1.0M),接着,在高压釜中加入上述溶液,从玻璃制吹入管使氮100NL/h、乙烯20NL/h的混合气体流通,开始聚合。 Added 1.0mmol of triisobutyl move in advance of the high pressure nitrogen flow father in a toluene solution (Al = 1.0M), then added to this solution in an autoclave, the glass blowing tube nitrogen 100NL / h, ethylene 20NL / h of gas mixture flow, to initiate polymerization. 作为聚合气氛中的P。 As the polymerization atmosphere P. = 1.5875、Pe = 0.1488,算出PE/PQ = 0.0937。 = 1.5875, Pe = 0.1488, the calculated PE / PQ = 0.0937. 氮/乙烯混合气体在聚合中也连续地供给,在常压下、40°C进行10分钟聚合后,添加少量异丁醇停止聚合。 After nitrogen / ethylene mixed gas was continuously fed during polymerization under normal pressure, 40 ° C for 10 minutes of polymerization, a small amount of isobutanol was added to terminate the polymerization. 在包含ImL盐酸的1.5L甲醇中加入聚合物溶液,使4-甲基-1-戊烯聚合物析出。 1.5L methanol was added to the polymer solution containing ImL of hydrochloric acid, 4-methyl-1-pentene polymer precipitated. 将其在80°C进行10小时减压干燥,结果得到4-甲基-1-戊烯聚合物1.03g。 Which was dried under reduced pressure for 10 hours at 80 ° C, the resulting 4-methyl-1-pentene polymer 1.03g. 聚合活性为1.55kg/mmol-Zr.hr,得到的4-甲基_1_ 戍烯聚合物的[η ]= 1.57dl/g、Tc = 200°C、Tm = 228。 The polymerization activity was 1.55kg / mmol-Zr.hr, 4- methyl pentene _1_ resulting polymer [η] = 1.57dl / g, Tc = 200 ° C, Tm = 228. . 、Δ H (Tm) = 19.2mJ/mg、乙烯含量=0.3% > [r] = 2.0% „ , Δ H (Tm) = 19.2mJ / mg, ethylene content = 0.3%> [r] = 2.0% "

[0227][参考例3] [0227] [Reference Example 3]

[0228] 从玻璃制吹入管使氮25NL/h、乙烯0.5NL/h的混合气体流通,开始聚合,聚合气氛中的PE/P。 [0228] from nitrogen blowing tube glass 25NL / h, the mixed gas of ethylene 0.5NL / h flow, to initiate polymerization, the polymerization atmosphere PE / P. = 0.0023,除此以外,按照参考例2进行实验。 = 0.0023, except that, in Reference Example 2 experiment.

[0229][参考例4] [0229] [Reference Example 4]

[0230] 从玻璃制吹入管使氮20NL/h、乙烯4NL/h的混合气体流通,开始聚合,聚合气氛中的ΡΕ/Ρο = 0.0190,除此以外,按照参考例2进行实验。 [0230] blown from a tube made of glass so that nitrogen 20NL / h, the mixed gas of ethylene 4NL / h flow, to initiate polymerization, the polymerization atmosphere ΡΕ / Ρο = 0.0190, except that, in Reference Example 2 experiment.

[0231] 在表1-1~表1-5中表示实施例1~11、比较例I~7、参考例I~4的结果。 [0231] Examples 1 to 11 represented in Tables 1-1 to 1-5, Comparative Examples I ~ 7, with reference to the results of Examples I ~ 4.

[0232][表 1-1] [0232] [Table 1-1]

[0233] [0233]

Figure CN102686615BD00261

[0234][表 1-2] [0234] [Table 1-2]

[0235] [0235]

Figure CN102686615BD00262

[0236][表 1-3] [0236] [Table 1-3]

Figure CN102686615BD00263

[0238][表 1-4] [0238] [Table 1-4]

Figure CN102686615BD00264

[0240][表 1-5] [0240] [Table 1-5]

Figure CN102686615BD00271

[0242] 过渡金属化合物: [0242] The transition metal compound:

[0243] al:二苄基亚甲基(环戊二烯基)(3,6_ 二叔丁基芴基)二氯化锆 [0243] al: zirconium dibenzylmethylene (cyclopentadienyl) (3,6_ di-tert-fluorenyl) dichloride

[0244] a2:二苄基亚甲基(环戊二烯基)(2,7_ 二对氯苯基_3,6_ 二叔丁基芴基)二氯化错 [0244] a2: dibenzylmethylene (cyclopentadienyl) (p-chlorophenyl _3,6_ two 2,7_ di-tert-fluorenyl) error dichloride

[0245] a3: 二苯基亚甲基(3_叔丁基_5_甲基环戊二烯基)(2,7_ 二叔丁基芴基)二氯化错 [0245] a3: diphenylmethylene (tert-butyl-3_ _5_ methylcyclopentadienyl) (2,7_ di-t-butyl-fluorenyl) di wrong dichloride

[0246] a4:二苄基亚甲基(环戊二烯基)(2,7_ 二苯基_3,6_ 二叔丁基芴基)二氯化锆 [0246] a4: dibenzylmethylene (cyclopentadienyl) (diphenyl _3,6_ 2,7_ di-tert-fluorenyl) zirconium dichloride

[0247] a5:二对氯苄基亚甲基(环戊二烯基)(2,7_ 二苯基_3,6_ 二叔丁基芴基)二氯化错 [0247] a5: two p-chlorobenzyl methylene (cyclopentadienyl) (diphenyl _3,6_ 2,7_ di-tert-fluorenyl) di wrong dichloride

[0248] 工业上的可利用性 [0248] INDUSTRIAL APPLICABILITY

[0249] 通过本发明,在工业上能够制造的条件下,能够以优异的聚合活性,制造高分子量且高熔点的间规立构α-烯烃聚合物,这一事实给予聚烯烃工业界的贡献很大。 [0249] By the present invention, under conditions that can be manufactured industrially, excellent polymerization activity can produce a high melting point and a high molecular weight syndiotactic α- olefin polymer, the contribution given to the fact that the polyolefin industry great. 例如,在将丙烯和乙烯作为单体使用时,虽然得到的间规立构聚丙烯包含微量源自乙烯的单元,但外消旋二单元组分率、分子量都高,维持着高熔点。 For example, when propylene and ethylene as a monomer, although the inter-obtained isotactic polypropylene contain minor amounts of units derived from ethylene, the racemic diad fraction, are high molecular weight, high melting maintained. 另外,使用丙烯以外的α-烯烃时,也同样地是在工业上能够制造外消旋二单元组分率、分子量都高且维持高熔点的间规立构α -烯烃聚合物等能够广泛应用的方法,非常有益。 Further, when using α- olefin other than propylene, it is likewise possible to manufacture industrially the racemic diad fraction, both high molecular weight and a high melting point to maintain syndiotactic α - olefin polymers and the like can be widely applied the method is very useful.

Claims (12)

  1. 1.一种间规立构α -烯烃聚合物的制造方法,其特征在于: 在包含(A)下述通式[I ]所示的过渡金属化合物、和(B)选自(b-2)与过渡金属化合物(A)反应形成离子对的化合物和(b-3)有机铝化合物中的至少I种化合物的烯烃聚合用催化剂的存在下,在聚合温度25°C以上的条件下聚合包含I种以上的碳原子数为3~10的α -烯烃和少量乙烯的单体时,将供给聚合器的乙烯摩尔数设为Pe,将碳原子数为3~10的α -烯烃摩尔数设为P0时,满足0.001 ^ ΡΕ/Ρ0 ( 0.030, 所述聚合物包含源自碳原子数为3~10的α-烯烃中的至少I种以上的结构单元X和源自乙烯的结构单元Y,满足全部下述条件[I]~[4]: [I ]将在聚合物中占有的结构单元X的含量设为X、单位为mol %,将在聚合物中占有的结构单元Y的含量设为y、单位为mol%时,98.5≤x≤99.9且1.5≤y≤0.1,且x+y =100 ; [2]由13C-NMR测定的外消旋二单元组分率([r])为90% A syndiotactic α - method for producing an olefin polymer, characterized by: containing (A) by the following general formula [I] a transition metal compound, and (B) is selected from (b-2 ) forming the transition metal compound (a) is reacted with in the presence of an olefin polymerization catalyst at least I compounds of the compound and (b-3) an organoaluminum compound ion pair is, at the polymerization temperatures above 25 ° C and polymerization comprising or more carbon atoms thereof is α 3 ~ 10 I - a small amount of olefin and vinyl monomer polymerization reactor ethylene was fed to the mole number Pe, the number of carbon atoms of α 3 ~ 10 - the number of moles of olefin provided is P0, satisfies 0.001 ^ ΡΕ / Ρ0 (0.030, said polymer comprising carbon atoms derived from α- olefin having 3 to 10 in at least a structural unit I species X derived from ethylene and a structural unit Y, all of the following conditions [I] satisfies ~ [4]: ​​[I] content in the polymer occupied by the structural unit X is defined as X, the unit of mol%, provided the content of the structural unit Y in the polymer will occupy when y, the unit of mol%, 98.5≤x≤99.9 and 1.5≤y≤0.1, and x + y = 100; [2] racemic diad fraction ([R & lt]) measured by 13C-NMR 90% ^ [r] < 100% ; [3]以135°C的十氢化萘溶液测得的特性粘度([η ])为0.70dl/g以上; [4]由差示扫描量热计(DSC)求出的熔点(Tm)为145°C以上, ^ [R] <100%; [3] in a decalin solution was measured to 135 ° C having an intrinsic viscosity ([[eta]]) of 0.70dl / g or more; [4] by a differential scanning calorimeter (DSC) determined point (Tm) less than 145 ° C,
    Figure CN102686615BC00021
    通式[I]中,R1 > R2> R3和R4的4个基团选自氢原子、烃基和含硅基,分别相同或不同,R1和R2不相互结合形成环,R3和R4不相互结合形成环,R5和R6为选自氢原子、碳原子数为2~20的烃基和含硅基中的原子或取代基,相互相同或不同,M选自钛原子、锆原子和铪原子,Q表示卤原子、烃基、碳原子数为10以下的中性的共轭二烯或非共轭二烯、阴离子配位基或能够以孤对电子配位的中性配位基,j表示I~4的整数,j为2以上时,多个存在的Q相互相同或不同。 Formula [I] in, R1> R2> R3 and R4 are 4 groups selected from a hydrogen atom, a hydrocarbon group and a silicon-containing, the same or different, R1, and R2 are not bonded to each other to form a ring, R3 and R4 are not bonded to each other atoms forming a ring, R5 and R6 are selected from a hydrogen atom, 2 to 20 carbon atoms and silicon-containing hydrocarbon group or a substituted group, the same or different, M is selected titanium atom, zirconium atom and hafnium atom, Q represents a halogen atom, a hydrocarbon group, the number of carbon atoms in a neutral conjugated diene of 10 or less or non-conjugated diene, anionic ligand group or a lone pair of electrons capable of coordinating neutral ligand, j represents I ~ 4 integer, j is 2 or more, plural Q the same or different.
  2. 2.如权利要求1所述的间规立构α-烯烃聚合物的制造方法,其特征在于:所述(b-3)有机铝化合物为(b-Ι)有机铝氧化合物。 A method for producing syndiotactic α- olefin polymer as claimed in claim 1, wherein: said (b-3) an organoaluminum compound (b-Ι) an organoaluminum oxy-compound.
  3. 3.如权利要求1所述的间规立构α-烯烃聚合物的制造方法,其特征在于:在所述通式[I]中,R2和R3为相同原子或相同基团。 A method for producing syndiotactic α- olefin polymer as claimed in claim 1, wherein: in the general formula [I],, R2 and R3 are the same atoms or the same groups.
  4. 4.如权利要求1所述的间规立构α-烯烃聚合物的制造方法,其特征在于:在所述通式[I]中,R2和R3为叔丁基。 A method for producing syndiotactic α- olefin polymer as claimed in claim 1, wherein: in the general formula [I],, R2 and R3 is tert-butyl.
  5. 5.如权利要求1所述的间规立构α-烯烃聚合物的制造方法,其特征在于: 在所述通式[I]中,R2和R3为叔丁基,R1和R4为氢原子或碳原子数为6~20的芳基,分别相同或不同。 A method for producing syndiotactic α- olefin polymer as claimed in claim 1, wherein: in the general formula [I],, R2 and R3 is t-butyl, R1, and R4 is a hydrogen atom carbon atoms, or aryl having 6 to 20 groups, the same or different.
  6. 6.如权利要求1所述的间规立构α-烯烃聚合物的制造方法,其特征在于:在所述通式[I]中,R5和R6为碳原子数为6~20的烃基,分别相同或不同。 A method for producing syndiotactic α- olefin polymer as claimed in claim 1, wherein: in the general formula [I],, R5 and R6 is a hydrocarbon group having a carbon number of 6 to 20, They are the same or different.
  7. 7.如权利要求1所述的间规立构α-烯烃聚合物的制造方法,其特征在于: 在所述通式[I ]中,R5和R6为碳原子数为6~20的芳基或碳原子数为6~20的芳烷基,分别相同或不同。 A method for producing syndiotactic α- olefin polymer as claimed in claim 1, wherein: in the general formula [I],, R5 and R6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 aralkyl group, the same or different.
  8. 8.如权利要求1所述的间规立构α-烯烃聚合物的制造方法,其特征在于: 在所述通式[I]中,R2和R3为叔丁基,R1和R4为氢原子或碳原子数为6~20的芳基,分别相同或不同,R5和R6为碳原子数为6~20的芳基或碳原子数为6~20的芳烷基,分别相同或不同。 A method for producing syndiotactic α- olefin polymer as claimed in claim 1, wherein: in the general formula [I],, R2 and R3 is t-butyl, R1, and R4 is a hydrogen atom carbon atoms, or aryl having 6 to 20 groups, the same or different, R5 and R6 carbon atoms or an aryl group having 6 to 20 carbon atoms and having 6 to 20 aralkyl group, the same or different.
  9. 9.如权利要求8所述的间规立构α-烯烃聚合物的制造方法,其特征在于:在所述通式[I]中,R5和R6为碳原子数为6~20的芳烷基。 A method for producing syndiotactic α- olefin polymer as claimed in claim 8, wherein: in the general formula [I],, R5 and R6 carbon atoms, aralkyl having 6 to 20 base.
  10. 10.如权利要求1~9中任一项所述的间规立构α-烯烃聚合物的制造方法,其特征在于: 所述碳原子数为3~10的α -烯烃中的至少I种为丙烯。 A method for producing syndiotactic α- olefin polymer as claimed in claim any one of 1 to 9, characterized in that: the number of carbon atoms of α 3 ~ 10 - Type I olefins least propylene.
  11. 11.一种间规立构α -烯烃聚合物的制造方法,其特征在于: 按照权利要求1所述的制造方法,连续地或间歇地向聚合器中供给乙烯和/或丙烯,将乙烯的摩尔数设为Pe,将丙烯的摩尔数设为P。 A syndiotactic α - method for producing an olefin polymer, wherein: said manufacturing method according to claim 1, continuously or intermittently feeding ethylene and / or propylene to the polymerization reactor, the ethylene to moles of Pe, the propylene to P. 时,0.001≤ΡΕ/Ρ0≤ 0.030。 When, 0.001≤ΡΕ / Ρ0≤ 0.030.
  12. 12.如权利要求1~9或11中任一项所述的间规立构α -烯烃聚合物的制造方法,其特征在于:所述碳原子数为3~10的α -烯烃中的至少I种为4-甲基-1-戊烯。 Olefins at least - the number of carbon atoms of α 3 ~ 10: The method of producing an olefin polymer, characterized by - 1 to 9 or 12. The syndiotactic α 11 in any one of claims Type I is 4-methyl-1-pentene.
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